Substituted phenylketoenols

ABSTRACT

The invention relates to novel phenyl-substituted cyclic ketoenols of the formula (I) 
                         
in which
     A, B, G, X, Y, Z and W are each as defined in the description,   to processes and intermediates for their preparation and to their use as pesticides and herbicides.

This application is a divisional application of U.S. patent applicationSer. No. 10/701,820 filed Nov. 5, 2003 now U.S. Pat. No. 6,900,341,which in turn was a divisional application of U.S. patent applicationSer. No. 10/404,723, filed Apr. 1, 2003, now U.S. Pat. No. 6,670,488,which in turn was a divisional application of U.S. Ser. No. 09/530,883,filed May 8, 2000, now U.S. Pat. No. 6,608,211, which in turn was thenational stage of PCT/EP98/068,666 filed Oct. 29, 1998, which in turnclaimed priority of German Patent Application No. 197 49 720.9, filedNov. 11, 1997.

The invention relates to novel phenyl-substituted cyclic ketoenols, to aplurality of processes and intermediates for their preparation and totheir use as pesticides and herbicides.

It is already known that certain phenyl-substituted cyclic ketoenols areactive as insecticides, acaricides and/or herbicides.

1H-Arylpyrrolidine-dione derivatives (EP-A-456 063, EP-A-521 334,EP-A-596 298, EP-A-613 884, EP-A-613 885, DE-44 40 594, DE-196 49 665,WO 94/01 997, WO 95/01 358, WO 95/20 572, EP-A-668 267, WO 95/26 954, WO96/25395, WO 96/35 664, WO 97/01 535 and WO 97/02 243) and their use aspesticides and, of some of them, as herbicides, are known.

However, the herbicidal, acaricidal and insecticidal activity and/orspectrum of activity and/or plant safety of these compounds, inparticular with respect to crop plants, is not always satisfactory.

This invention, accordingly, provides novel compounds of the formula (I)

in which

-   W represents hydrogen, cyano, nitro, halogen, alkyl, alkenyl,    alkinyl, alkoxy, halogenoalkyl, halogenoalkoxy or represents phenyl,    phenoxy, phenylthio, phenylalkoxy or phenylalkylthio, each of which    is optionally substituted,-   X represents halogen, alkyl, alkenyl, alkinyl, alkoxy, alkenyloxy,    halogenoalkyl, halogenoalkoxy, halogenoalkenyloxy, cyano, nitro or    represents phenyl, phenoxy, phenylthio, phenylalkyloxy or    phenylalkylthio, each of which is optionally substituted,-   Y represents hydrogen, halogen, alkyl, alkoxy, halogenoalkyl,    halogenoalkoxy, cyano or nitro,-   Z represents hydrogen, halogen, alkyl, alkoxy, halogenoalkyl,    halogenoalkoxy, hydroxyl, cyano, nitro or represents phenoxy,    phenylthio, 5- or 6-membered hetaryloxy, 5- or 6-membered    hetarylthio, phenylalkyloxy or phenylalkylthio, each of which is    optionally substituted,-   A represents alkyl or optionally substituted phenyl,-   B represents hydrogen or alkyl,-   G represents hydrogen (a) or one of the radicals

-    in which    -   E represents a metal ion equivalent or an ammonium ion,    -   L represents oxygen or sulphur,    -   M represents oxygen or sulphur,-   R¹ represents alkyl, alkenyl, alkoxyalkyl, alkylthioalkyl or    polyalkoxyalkyl, each of which is optionally substituted by halogen    or cyano, or represents cycloalkyl or heterocyclyl, each of which is    optionally substituted by halogen, alkyl or alkoxy, or represents    phenyl, phenylalkyl, hetaryl, phenoxyalkyl or hetaryloxyalkyl, each    of which is optionally substituted,-   R² represents alkyl, alkenyl, alkoxyalkyl or polyalkoxyalkyl, each    of which is optionally substituted by halogen or cyano, or    represents cycloalkyl, phenyl or benzyl, each of which is optionally    substituted,-   R³, R⁴ and R⁵ independently of one another each represent alkyl,    alkoxy, alkylamino, dialkylamino, alkylthio, alkenylthio or    cycloalkylthio, each of which is optionally substituted by halogen,    or represent phenyl, benzyl, phenoxy or phenylthio, each of which is    optionally substituted,-   R⁶ and R⁷ independently of one another each represent hydrogen,    represent alkyl, cycloalkyl, alkenyl, alkoxy, alkoxyalkyl, each of    which is optionally substituted by halogen or cyano, represent    phenyl or benzyl, each of which is optionally substituted, or    together with the linking N atom form a cycle which optionally    contains oxygen or sulphur and which is optionally substituted.

The compounds of the formula (I) can be present, depending, inter alia,on the nature of the substituents, as optical isomers or isomer mixturesof differing composition which, if appropriate, can be separated in acustomary manner. Both the pure isomers and the isomer mxtures, theirpreparation and use, and compositions comprising them are part of thesubject matter of the present invention. In the following, forsimplicity, however, compounds of the formula (I) are always referredto, although both pure compounds and, if appropriate, mixtures havingdifferent proportions of isomeric compounds are intended.

Including the various meanings (a), (b), (c), (d), (e), (f) and (g) ofthe group G, the following principal structures (I-a) to (I-g) result:

in which

-   A, B, E, L, M, W, X, Y, Z, R¹, R², R³, R⁴, R⁵, R⁶ and R⁷ are each as    defined above.

Furthermore, it has been found that the novel compounds of the formula(I) are obtained by one of the processes described below:

-   (A) Compounds of the Formula (I-a)

-    in which    -   A, B, W, X, Y and Z are each as defined above, are obtained when        compounds of the formula (II)

-   -    in which    -   A, B, W, X, Y and Z are each as defined above, and    -   R⁸ represents alkyl (preferably C₁–C₆-alkyl), are        intramolecularly condensed in the presence of a diluent and in        the presence of a base.

Furthermore, it has been found

-   (B) that the compounds of the formula (I-b) shown above in which R¹,    A, B, W, X, Y and Z are each as defined above are obtained when    compounds of the formula (I-a) shown above in which A, B, W, X, Y    and Z are each as defined above,    -   α) are reacted with acyl halides of the formula (III)

-   -    in which        -   R¹ is as defined above and        -   Hal represents halogen (in particular chlorine or bromine)            or    -   β) are reacted with carboxylic anhydrides of the formula (IV)        R¹—CO—O—CO—R¹  (IV)    -    in which        -   R¹ is as defined above,    -   if appropriate in the presence of a diluent and if appropriate        in the presence of an acid binder;

-   (C) that the compounds of the formula (I-c) shown above in which R²,    A, B, W, M, X, Y and Z are each as defined above and L represents    oxygen are obtained when compounds of the formula (I-a) shown above    in which A, B, W, X, Y and Z are each as defined above,    -   are reacted with chloroformic esters or chloroformic thioesters        of the formula (V)        R²-M-CO—Cl  (V)    -    in which    -   R² and M are each as defined above,    -   if appropriate in the presence of a diluent and if appropriate        in the presence of an acid binder;

-   (D) that compounds of the formula (I-c) shown above in which R², A,    B, W, M, X, Y and Z are each as defined above and L represents    sulphur are obtained when compounds of the formula (I-a) shown above    in which A, B, W, X, Y and Z are each as defined above,    -   are reacted with chloromonothioformic esters or        chlorodithioformic esters of the formula (VI)

-   -    in which    -   M and R² are each as defined above,    -   if appropriate in the presence of a diluent and if appropriate        in the presence of an acid binder;

-   (E) that compounds of the formula (I-d) shown above in which R³, A,    B, W, X, Y and Z are each as defined above are obtained when    compounds of the formula (I-a) shown above in which A, B, W, X, Y    and Z are each as defined above,    -   are reacted with sulphonyl chlorides of the formula (VII)        R³—SO₂—Cl  (VII)    -    in which    -   R³ is as defined above,    -   if appropriate in the presence of a diluent and if appropriate        in the presence of an acid binder,

-   (F) that compounds of the formula (I-e) shown above in which L, R⁴,    R⁵, A, B, W, X, Y and Z are each as defined above are obtained when    compounds of the formula (I-a) shown above in which A, B, W, X, Y    and Z are each as defined above,    -   are reacted with phosphorus compounds of the formula (VIII)

-   -    in which    -   L, R⁴ and R⁵ are each as defined above and    -   Hal represents halogen (in particular chlorine or bromine),    -   if appropriate in the presence of a diluent and if appropriate        in the presence of an acid binder;

-   (G) that compounds of the formula (I-f) shown above in which E, A,    B, W, X, Y and Z are each as defined above are obtained when    compounds of the formula (I-a) in which A, B, W, X, Y and Z are each    as defined above,    -   are reacted with metal compounds or amines of the formulae (IX)        or (X)        Me(OR⁹)_(t)  (IX)

-   -    in which    -   Me represents a mono- or divalent metal (preferably an alkali        metal or alkaline earth metal such as lithium, sodium,        potassium, magnesium or calcium),    -   t represents the number 1 or 2 and    -   R⁹, R¹⁰, R¹¹ independently of one another each represent        hydrogen or alkyl (preferably C₁–C₈-alkyl),    -   if appropriate in the presence of a diluent;

-   (H) that compounds of the formula (I-g) shown above in which L, R⁶,    R⁷, A, B, W, X, Y and Z are each as defined above are obtained when    compounds of the formula (I-a) shown above in which A, B, W, X, Y    and Z are each as defined above,    -   α) are reacted with isocyanates or isothiocyanates of the        formula (XI)        R⁶—N═C=L  (XI)    -    in which    -   R⁶ and L are each as defined above,    -   if appropriate in the presence of a diluent and if appropriate        in the presence of a catalyst, or    -   β) are reacted with carbamoyl chlorides or thiocarbamoyl        chlorides of the formula (XII)

-   -    in which    -   L, R⁶ and R⁷ are each as defined above,    -   if appropriate in the presence of a diluent and if appropriate        in the presence of an acid binder.

Furthermore, it has been found that the novel compounds of the formula(I) have very good activity as pesticides, preferably as insecticidesand as acaricides, and as herbicides, and that they are additionallyfrequently very well tolerated by plants, in particular by crop plants.

The formula (I) provides a general definition of the compounds accordingto the invention. Preferred substituents and/or ranges of the radicalslisted in the formula mentioned hereinabove and hereinbelow areillustrated below:

-   W preferably represents hydrogen, nitro, cyano, halogen,    C₁–C₆-alkyl, C₂–C₆-alkenyl, C₂–C₆-alkinyl, C₁–C₆-alkoxy,    C₁–C₄-halogenoalkyl or C₁–C₄-halogenoalkoxy.-   X preferably represents halogen, C₁–C₆-alkyl, C₂–C₆-alkenyl,    C₂–C₆-alkinyl, C₁–C₆-alkoxy, C₃–C₆-alkenyloxy, C₁–C₄-halogenoalkyl,    C₁–C₄-halogenoalkoxy, C₂–C₆-halogenoalkenyloxy, cyano, nitro or    represents phenyl, phenoxy, phenylthio, phenyl-C₁–C₄-alkoxy or    phenyl-C₁–C₄-alkylthio, each of which is optionally substituted by    halogen, C₁–C₆-alkyl, C₁–C₆-alkoxy, C₁–C₄-halogenoalkyl,    C₁–C₄-halogenoalkoxy, nitro or cyano.-   Y preferably represents hydrogen, halogen, C₁–C₆-alkyl C₁–C₆-alkoxy,    C₁–C₄-halogenoalkyl, C₁–C₄-halogenoalkoxy, cyano or nitro.-   Z preferably represents hydrogen, halogen, C₁–C₆-alkyl,    C₁–C₆-alkoxy, C₁–C₄-halogenoalkyl, C₁–C₄-halogenoalkoxy, hydroxyl,    cyano, nitro or represents phenoxy, phenylthio, thiazolyloxy,    pyridinyloxy, pyrimidyloxy, pyrazolyloxy, phenyl-C₁–C₄-alkyloxy or    phenyl-C₁–C₄-alkylthio, each of which is optionally substituted by    halogen, C₁–C₄-alkyl, C₁–C₄-alkoxy, C₁–C₄-halogenoalkyl,    C₁–C₄-halogenalkoxy, nitro or cyano.-   A preferably represents C₁–C₆-alkyl or represents phenyl which is    optionally substituted by halogen, C₁–C₄-alkyl, C₁–C₄-alkoxy, nitro    or cyano.-   B preferably represents hydrogen or C₁–C₆-alkyl.-   G preferably represents hydrogen (a) or represents one of the    radicals

-    in which    -   E represents a metal ion equivalent or an ammonium ion,    -   L represents oxygen or sulphur and    -   M represents oxygen or sulphur.-   R¹ preferably represents C₁–C₂₀-alkyl, C₂–C₂₀-alkenyl,    C₁–C₈-alkoxy-C₁–C₈-alkyl, C₁–C₈-alkylthio-C₁–C₈-alkyl or    poly-C₁–C₈-alkoxy-C₁–C₈-alkyl, each of which is optionally    substituted by halogen or cyano, or represents C₃–C₈-cycloalkyl in    which optionally one or two not directly adjacent methylene groups    are replaced by oxygen and/or sulphur and which is optionally    substituted by halogen, C₁–C₆-alkyl or C₁–C₆-alkoxy,    -   represents phenyl which is optionally substituted by halogen,        cyano, nitro, C₁–C₆-alkyl, C₁–C₆-alkoxy, C₁–C₆-halogenoalkyl,        C₁–C₆-halogenoalkoxy, C₁–C₆-alkylthio or C₁–C₆-alkylsulfonyl,    -   represents phenyl-C₁–C₆-alkyl which is optionally substituted by        halogen, nitro, cyano, C₁–C₆-alkyl, C₁–C₆-alkoxy,        C₁–C₆-halogenoalkyl or C₁–C₆-halogenoalkoxy,    -   represents 5- or 6-membered hetaryl having one or two hetero        atoms selected from the group consisting of oxygen, sulphur and        nitrogen (for example pyrazolyl, thiazolyl, pyridyl, pyrimidyl,        furanyl or thienyl) which is optionally substituted by halogen        or C₁–C₆-alkyl,    -   represents phenoxy-C₁–C₆-alkyl which is optionally substituted        by halogen or C₁–C₆-alkyl or    -   represents 5- or 6-membered hetaryloxy-C₁–C₆-alkyl having one or        two hetero atoms selected from the group consisting of oxygen,        sulphur and nitrogen (for example pyridyloxy-C₁–C₆-alkyl,        pyrimidyloxy-C₁–C₆-alkyl or thiazolyloxy-C₁–C₆-alkyl) which is        optionally substituted by halogen, amino or C₁–C₆-alkyl.-   R² preferably represents C₁–C₂₀-alkyl, C₂–C₂₀-alkenyl,    C₁–C₈-alkoxy-C₂–C₈-alkyl or poly-C₁–C₈-alkoxy-C₂–C₈-alkyl, each of    which is optionally substituted by halogen or cyano,    -   represents C₃–C₈-cycloalkyl which is optionally substituted by        halogen, C₁–C₆-alkyl or C₁–C₆-alkoxy or    -   represents phenyl or benzyl, each of which is optionally        substituted by halogen, cyano, nitro, C₁–C₆-alkyl, C₁–C₆-alkoxy,        C₁–C₆-halogenoalkyl or C₁–C₆-halogenoalkoxy.-   R³ preferably represents C₁–C₈-alkyl which is optionally substituted    by halogen or represents phenyl or benzyl, each of which is    optionally substituted by halogen, C₁–C₆-alkyl, C₁–C₆-alkoxy,    C₁–C₄-halogenoalkyl, C₁–C₄-halogenoalkoxy, cyano or nitro.-   R⁴ and R⁵ independently of one another each preferably represent    C₁–C₈-alkyl, C₁–C₈-alkoxy, C₁–C₈-alkylamino, di-(C₁–C₈-alkyl)amino,    C₁–C₈-alkylthio or C₃–C₈-alkenylthio, each of which is optionally    substituted by halogen, or represents phenyl, phenoxy or phenylthio,    each of which is optionally substituted by halogen, nitro, cyano,    C₁–C₄-alkoxy, C₁–C₄-halogenoalkoxy, C₁–C₄-alkylthio,    C₁–C₄-halogenoalkylthio, C₁–C₄-alkyl or C₁–C₄-halogenoalkyl.-   R⁶ and R⁷ independently of one another each preferably represent    hydrogen, represent C₁–C₈-alkyl, C₃–C₈-cycloalkyl, C₁–C₈-alkoxy,    C₃–C₈-alkenyl, C₁–C₈-alkoxy-C₂–C₈-alkyl, each of which is optionally    substituted by halogen or cyano or represents phenyl or benzyl, each    of which is optionally substituted by halogen, C₁–C₈-alkyl,    C₁–C₈-halogenoalkyl or C₁–C₈-alkoxy, or together represent a    C₃–C₆-alkylene radical in which optionally one methylene group is    replaced by oxygen or sulphur and which is optionally substituted by    C₁–C₆-alkyl.-   W particularly preferably represents hydrogen, nitro, cyano,    fluorine, chlorine, bromine, C₁–C₄-alkyl, C₁–C₄-alkoxy,    C₁–C₂-halogenoalkyl or C₁–C₂-halogenoalkoxy.-   X particularly preferably represents fluorine, chlorine, bromine,    C₁–C₄-alkyl, C₁–C₄-alkoxy, C₃–C₄-alkenyloxy, C₁–C₂-halogenoalkyl,    C₁–C₂-halogenoalkoxy, C₂–C₄-halogenoalkenyloxy, cyano, nitro or    represents phenyl or benzyloxy, each of which is optionally    substituted by fluorine, chlorine, bromine, C₁–C₄-alkyl,    C₁–C₄-alkoxy, C₁–C₂-halogenoalkyl, C₁–C₂-halogenoalkoxy, nitro or    cyano.-   Y particularly preferably represents hydrogen, fluorine, chlorine,    bromine, C₁–C₄-alkyl, C₁–C₄-alkoxy, C₁–C₂-halogenoalkyl,    C₁–C2-halogenoalkoxy, cyano or nitro.-   Z particularly preferably represents hydrogen, fluorine, chlorine,    bromine, C₁–C₄-alkyl, C₁–C₄-alkoxy, C₁–C₂-halogenoalkyl,    C₁–C₂-halogenoalkoxy, hydroxyl, cyano, nitro or represents phenoxy    or benzyloxy, each of which is optionally substituted by fluorine,    chlorine, bromine, C₁–C₄-alkyl, C₁–C₄-alkoxy, C₁–C₂-halogenoalkyl,    C₁–C₂-halogenoalkoxy, nitro or cyano.-   A particularly preferably represents C₁–C₄-alkyl or represents    phenyl.-   B particularly preferably represents hydrogen, methyl or ethyl.-   G particularly preferably represents hydrogen (a) or represents one    of the radicals

-    (in particular represents one of the radicals (a), (b) or (c)), in    which    -   E represents a metal ion equivalent or an ammonium ion,    -   L represents oxygen or sulphur and    -   M represents oxygen or sulphur.-   R¹ particularly preferably represents C₁–C₁₆-alkyl, C₂–C₁₆-alkenyl,    C₁–C₆-alkoxy-C₁–C₆-alkyl, C₁–C₆-alkylthio-C₁–C₆-alkyl or    poly-C₁–C₆-alkoxy-C₁–C₆-alkyl, each of which is optionally    substituted by fluorine, chlorine, or represents C₃–C₇-cycloalkyl in    which optionally one or two not directly adjacent methylene groups    are replaced by oxygen and/or sulphur and which is optionally    substituted by fluorine, chlorine, C₁–C₅-alkyl or C₁–C₅-alkoxy,    -   represents phenyl, which is optionally substituted by fluorine,        chlorine, bromine, cyano, nitro, C₁–C₄-alkyl, C₁–C₄-alkoxy,        C₁–C₃-halogenoalkyl, C₁–C₃-halogenoalkoxy, C₁–C₄-alkylthio or        C₁–C₄-alkylsulphonyl,    -   represents phenyl-C₁–C₄-alkyl which is optionally substituted by        fluorine, chlorine, bromine, C₁–C₄-alkyl, C₁–C₄-alkoxy,        C₁–C₃-halogenoalkyl or C₁–C₃-halogenoalkoxy,    -   represents pyrazolyl, thiazolyl, pyridyl, pyrimidyl, furanyl or        thienyl, each of which is optionally substituted by fluorine,        chlorine, bromine or C₁–C₄-alkyl,    -   represents phenoxy-C₁–C₅-alkyl which is optionally substituted        by fluorine, chlorine, bromine or C₁–C₄-alkyl or    -   represents pyridyloxy-C₁–C₅-alkyl, pyrimidyloxy-C₁–C₅-alkyl or        thiazolyloxy-C₁–C₅-alkyl, each of which is optionally        substituted by fluorine, chlorine, bromine, amino or        C₁–C₄-alkyl.-   R² particularly preferably represents C₁–C₁₆-alkyl, C₂–C₁₆-alkenyl,    C₁–C₆-alkoxy-C₂–C₆-alkyl or poly-C₁–C₆-alkoxy-C₂–C₆-alkyl, each of    which is optionally substituted by fluorine or chlorine,    -   represents C₃–C₇-cycloalkyl which is optionally substituted by        fluorine, chlorine, C₁–C₄-alkyl or C₁–C₄-alkoxy or    -   represents phenyl or benzyl, each of which is optionally        substituted by fluorine, chlorine, bromine, cyano, nitro,        C₁–C₄-alkyl, C₁–C₃-alkoxy, C₁–C₃-halogenoalkyl or        C₁–C₃-halogenoalkoxy.-   R³ particularly preferably represents C₁–C₆-alkyl which is    optionally substituted by fluorine or chlorine or represents phenyl    or benzyl, each of which is optionally substituted by fluorine,    chlorine, bromine, C₁–C₄-alkyl, C₁–C₄-alkoxy, C₁–C₂-halogenoalkoxy,    C₁–C₂-halogenoalkyl, cyano or nitro.-   R⁴ and R⁵ independently of one another particularly preferably    represent C₁–C₆-alkyl, C₁–C₆-alkoxy, C₁–C₆-alkylamino,    di-(C₁–C₆-alkyl)amino, C₁–C₆-alkylthio or C₃–C₄-alkenylthio, each of    which is optionally substituted by fluorine or chlorine, or    represent phenyl, phenoxy or phenylthio, each of which is optionally    substituted by fluorine, chlorine, bromine, nitro, cyano,    C₁–C₃-alkoxy, C₁–C₃-halogenoalkoxy, C₁–C₃-alkylthio,    C₁–C₃-halogenoalkylthio, C₁–C₃-alkyl or C₁–C₃-halogenoalkyl.-   R⁶ and R⁷ independently of one another particularly preferably    represent hydrogen, represent C₁–C₆-alkyl, C₃–C₆-cycloalkyl,    C₁–C₆-alkoxy, C₃–C₆-alkenyl or C₁–C₆-alkoxy-C₂–C₆-alkyl, each of    which is optionally substituted by fluorine or chlorine, or    represent phenyl or benzyl, each of which is optionally substituted    by fluorine, chlorine, bromine, C₁–C₅-halogenoalkyl, C₁–C₅-alkyl or    C₁–C₅-alkoxy, or together represent a C₃–C₆-alkylene radical in    which optionally one methylene group is replaced by oxygen or    sulphur and which is optionally substituted by C₁–C₄-alkyl.

In the radical definitions referred to as being (particularly)preferred, halogen in combination with other radicals (for example inhalogenoalkyl, halogenoalkoxy or halogenoalkenyloxy) in particularrepresents fluorine, chlorine and bromine, specifically fluorine andchlorine.

-   W very particularly preferably represents hydrogen, nitro, cyano,    fluorine, chlorine, bromine, methyl, ethyl, n-propyl, isopropyl,    n-butyl, isobutyl, methoxy, ethoxy, n-propoxy, isopropoxy,    trifluoromethyl, difluoromethoxy or trifluoromethoxy.-   X very particularly preferably represents fluorine, chlorine,    bromine, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl,    methoxy, ethoxy, n-propoxy, isopropoxy, trifluoromethyl,    trifluoromethoxy, difluoromethoxy, cyano or nitro.-   Y very particularly preferably represents hydrogen, fluorine,    chlorine, bromine, methyl, ethyl, n-propyl, isopropyl, n-butyl,    isobutyl, tert-butyl, methoxy, ethoxy, n-propoxy, isopropoxy,    trifluoromethyl, trifluoromethoxy, difluoromethoxy, cyano or nitro.-   Z very particularly preferably represents hydrogen, fluorine,    chlorine, bromine, methyl, ethyl, n-propyl, isopropyl, n-butyl,    isobutyl, tert-butyl, methoxy, ethoxy, n-propoxy, isopropoxy,    trifluoromethyl, trifluoromethoxy, difluoromethoxy, cyano or nitro.-   A very particularly preferably represents methyl or ethyl.-   B very particularly preferably represents hydrogen or methyl.-   G very particularly preferably represents hydrogen (a) or represents    one of the radicals

-    (in particular represents one of the radicals (a), (b) or (c)), in    which    -   E represents a metal ion equivalent or an ammonium ion,    -   L represents oxygen or sulphur and    -   M represents oxygen or sulphur.-   R¹ very particularly preferably represents C₁–C₁₄-alkyl,    C₂–C₁₄-alkenyl, C₁–C₄-alkoxy-C₁–C₆-alkyl,    C₁–C₄-alkylthio-C₁–C₆-alkyl, poly-C₁–C₄-alkoxy-C₁–C₄-alkyl, each of    which is optionally substituted by fluorine or chlorine, or    represents C₃–C₆-cycloalkyl in which optionally one or two not    directly adjacent methylene groups are replaced by oxygen and/or    sulphur and which is optionally substituted by fluorine, chlorine,    methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, tert-butyl,    methoxy, ethoxy, n-propoxy or isopropoxy,    -   represents phenyl which is optionally substituted by fluorine,        chlorine, bromine, cyano, nitro, methyl, ethyl, n-propyl,        i-propyl, methoxy, ethoxy, trifluoromethyl, trifluoromethoxy,        methylthio, ethylthio, methylsulphonyl or ethylsulphonyl,    -   represents benzyl which is optionally substituted by fluorine,        chlorine, bromine, methyl, ethyl, n-propyl, i-propyl, methoxy,        ethoxy, trifluoromethyl or trifluoromethoxy,    -   represents furanyl, thienyl or pyridyl, each of which is        optionally substituted by fluorine, chlorine, bromine, methyl or        ethyl,    -   represents phenoxy-C₁–C₄-alkyl which is optionally substituted        by fluorine, chlorine, methyl or ethyl or    -   represents pyridyloxy-C₁–C₄-alkyl, pyrimidyloxy-C₁–C₄-alkyl or        thiazolyloxy-C₁–C₄-alkyl, each of which is optionally        substituted by fluorine, chlorine, amino, methyl or ethyl.-   R² very particularly preferably represents C₁–C₁₄-alkyl,    C₂–C₁₄-alkenyl, C₁–C₄-alkoxy-C₂–C₆-alkyl or    poly-C₁–C₄-alkoxy-C₂–C₆-alkyl, each of which is optionally    substituted by fluorine or chlorine,    -   represents C₃–C₆-cycloalkyl which is optionally substituted by        fluorine, chlorine, methyl, ethyl, n-propyl, isopropyl or        methoxy,    -   or represents phenyl or benzyl, each of which is optionally        substituted by fluorine, chlorine, cyano, nitro, methyl, ethyl,        n-propyl, i-propyl, methoxy, ethoxy, trifluoromethyl or        trifluoromethoxy.-   R³ very particularly preferably represents methyl, ethyl, n-propyl,    isopropyl, n-butyl, tert-butyl, each of which is optionally    substituted by fluorine or chlorine, or represents phenyl or benzyl,    each of which is optionally substituted by fluorine, chlorine,    bromine, methyl, ethyl, isopropyl, tert-butyl, methoxy, ethoxy,    isopropoxy, trifluoromethyl, trifluoromethoxy, cyano or nitro.-   R⁴ and R⁵ independently of one another each very particularly    preferably represent C₁–C₄-alkyl, C₁–C₄-alkoxy, C₁–C₄-alkylamino,    di-(C₁–C₄-alkyl)amino or C₁–C₄-alkylthio, each of which is    optionally substituted by fluorine or chlorine, or represent phenyl,    phenoxy or phenylthio, each of which is optionally substituted by    fluorine, chlorine, bromine, nitro, cyano, methyl, methoxy,    trifluoromethyl or trifluoromethoxy.-   R⁶ and R⁷ independently of one another each very particularly    preferably represent hydrogen, represent C₁–C₄-alkyl,    C₃–C₆-cycloalkyl, C₁–C₄-alkoxy, C₃–C₄-alkenyl,    C₁–C₄-alkoxy-C₂–C₄-alkyl, each of which is optionally substituted by    fluorine or chlorine, or represent phenyl or benzyl, each of which    is optionally substituted by fluorine, chlorine, bromine, methyl,    methoxy or trifluoromethyl, or together represent a C₅–C₆-alkylene    radical in which optionally one methylene group is replaced by    oxygen or sulphur and which is optionally substituted by methyl or    ethyl.

Especially preferred are compounds of the formula (I), in which Arepresents CH₃ and B represents hydrogen, in particular in combinationwith the very particularly preferred radicals mentioned for G.

The abovementioned general or preferred definitions of radicals orillustrations can be combined with each other as desired, that is to saycombinations between the ranges and preferred ranges in question arealso possible. They apply both to the end products and, correspondingly,to the starting materials and intermediates.

Preference according to the invention is given to those compounds of theformula (I) which contain a combination of the definitions given aboveas being preferred (preferable).

Particular preference according to the invention is given to thosecompounds of the formula (I) which contain a combination of thedefinitions given above as being particularly preferred.

Very particular preference according to the invention is given to thosecompounds of the formula (I) which contain a combination of thedefinitions given above as being very particularly preferred.

Saturated or unsaturated hydrocarbon radicals such as alkyl or alkenylmay be, also in connection with hetero atoms such as, for example, inalkoxy, in each case straight-chain or branched as far as this ispossible.

Optionally substituted radicals may be mono- or polysubstituted, itbeing possible for the substituents in the case of polysubstitutions tobe identical or different.

In addition to the compounds mentioned in the Preparation Examples, thefollowing compounds of the formula (I-a) may be mentioned specifically:

TABLE 1 A = CH₃; B = H (I-a)

X W Y Z Br H Cl H Cl H Br H Cl H Cl H Cl H F H F H Cl H Cl H OCH₃ H Cl HCH₃ H OCH₃ H Cl H OCH₃ H OCH₃ H CH₃ H Cl H CH₃ H F H CH₃ H OCH₃ H CH₃ Ht-C₄H₉ H CH₃ H CH₃ H Cl Cl H H Cl F H H Cl OCH₃ H H Cl CH₃ H H Cl OC₂H₅H H OCH₃ OCH₃ H H CH₃ CH₃ H H Br CH₃ Br H Cl Cl CH₃ H CH₃ Br CH₃ H CH₃Cl CH₃ H CH₃ OCHF₂ CH₃ H CH₃ OCH₂CF₃ CH₃ H CH₃ OC₂H₅ CH₃ H CH₃ OCH₃ CH₃H CH₃ CH₃ CH₃ H Br Br CH₃ H Cl Cl CH₃ H C₂H₅ C₂H₅ Br H CH₃ CH₃ Br H CH₃CH₃ OCH₃ H Br Cl CH₃ H Br CH₃ Cl H Cl CH₃ Br H C₂H₅ Br CH₃ H CH₃ O—C₃H₇CH₃ H CH₃ CH₃ Cl H Cl H Cl Cl CH₃ H CH₃ CH₃ CH₃ H Cl CH₃ Br H Cl CH₃ BrH CH₃ CH₃ Cl H Br CH₃ Cl H Cl CH₃ CH₃ H Br CH₃ Cl H Cl F Cl H CH₃ Cl CH₃H H H Cl H H H Br H H H CF₃ H H H OCH₃ H H H CH₃ CH₃ CH₃ CH₃ CH₃ H CH₃CH₃ CH₃ CH₃ H CH₃ CH₃ CH₃ CH₃ F CH₃ CH₃ CH₃ Cl CH₃ CH₃ CH₃ Br CH₃ CH₃ HCl CH₃ CH₃ H Br Cl Cl H Br

Using according to process (A)N-[(4-chloro-2,6-dimethyl)-phenylacetyl]-4-amino-4-carboxyethyl-2-methyl-tetrahydropyranas starting material, the course of the process according to theinvention can be represented by the following equation:

Using according to process (Bα)3-[(2-chloro-4-methyl)-phenyl]-5,5-[(2-ethyl)-ethyleneoxyethyl]-pyrrolidine-2,4-dioneand pivaloyl chloride as starting materials, the course of the processaccording to the invention can be represented by the following equation:

Using according to process (B) (variant β)3-[(2,4-dichloro)-phenyl]-5,5-[(2-methyl)-ethyleneoxyethyl]-pyrrolidine-2,4-dioneand acetic anhydride as starting materials, the course of the processaccording to the invention can be represented by the following equation:

Using according to process (C)8-[(2,4-dichloro)-phenyl]-5,5-[(2-methyl)-ethyleneoxyethyl]-pyrrolidine-2,4-dioneand ethoxyethyl chloroformate as starting materials, the course of theprocess according to the invention can be represented by the followingequation:

Using according to process (D)3-[(2,6-dibromo-4-methyl)-phenyl]-5,5-[(2-ethyl)-ethyleneoxyethyl]-pyrrolidine-2,4-dioneand methyl chloromonothioformate as starting materials, the course ofthe reaction can be represented as follows:

Using according to process (E)2-[(2,4,6-trimethyl)-phenyl]-5,5-[(2-methyl)-ethyleneoxyethyl]-pyrrolidine-2,4-dioneand methanesulphonyl chloride as starting materials, the course of thereaction can be represented by the following equation:

Using according to process (F)2-[(4-bromo-2-chloro-6-methyl)-phenyl]-4-hydroxy-5,5-[(2-methyl)-ethyleneoxyethyl]-pyrrolidine-2,4-dioneand (2,2,2-trifluoroethyl) methanethio-phosphonyl chloride as startingmaterials, the course of the reaction can be represented by thefollowing equation:

Using according to process (G)3-[(2,4-dichloro)-6-methylphenyl]-5,5-[(2-ethyl)-ethyleneoxyethyl]-pyrrolidine-2,4-dioneand NaOH as components, the course of the process according to theinvention can be represented by the following equation:

Using according to process (H) (variant α)3-[(2-chloro-4-bromo-5-methyl)-phenyl]-4-hydroxy-5,5-[(2-methyl)-ethyleneoxyethyl]-pyrrolidine-2,4-dioneand ethyl isocyanate as starting materials, the course of the reactioncan be represented by the following equation:

Using according to process (H) (variant β)3-[(2-chloro-4,6-dimethyl)-phenyl]-5,5-[(2-methyl)-ethyleneoxyethyl]-pyrrolidine-2,4-dioneand dimethylcarbamidoyl chloride as starting materials, the course ofthe reaction can be represented by the following equation:

The compounds of the formula (II) required as starting materials in theprocess (A) according to the invention

in which

-   A, B, W, X, Y, Z and R⁸ are each as defined above, are novel.

The acylamino acid esters of the formula (II) are obtained, for example,when amino acid derivatives of the formula (XIII)

in which

-   A, B and R⁸ are each as defined above, are acylated with substituted    phenylacetyl halides of the formula (XIV)

in which

-   W, X, Y and Z are each as defined above and Hal represents chlorine    or bromine, (Chem. Reviews 52, 237–416 (1953); Bhattacharya,    Indian J. Chem. 6, 341–5, 1968) or when acylamino acids of the    formula (XV)

in which

-   A, B, W, X, Y and Z are each as defined above, are esterified (Chem.    Ind. (London) 1568 (1968)).

The Compounds of the Formula (XV)

in which

-   A, B, W, X, Y and Z are each as defined above, are novel.

The compounds of the formula (XV) are obtained, for example, when4-amino-tetrahydropyran-4-carboxylic acids of the formula (XVI)

in which

-   A and B are each as defined above are acylated according to    Schotten-Baumann (Organikum, VEB Deutscher Verlag der    Wissenschaften, Berlin 1977, P. 505) with substituted phenylacetyl    halides of the formula (XIV)

in which

-   W, X, Y and Z are each as defined above and Hal represents chlorine    or bromine.

Some of the compounds of the formula (XIV) are novel and can be preparedby known processes (cf., for example, DE-196 49 665).

The compounds of the formula (XIV) are obtained, for example, byreacting substituted phenylacetic acids of the formula (XVII)

in which

-   W, X, Y and Z are each as defined above with halogenating agents    (for example thionyl chloride, thionyl bromide, oxalyl chloride,    phosgene, phosphorus trichloride, phosphorus tribromide or    phosphorus pentachloride), if appropriate in the presence of a    diluent (for example optionally chlorinated aliphatic or aromatic    hydrocarbons such as toluene or methylene chloride) at temperatures    of from −20° C. to 150° C., preferably of from −10° C. to 100° C.

Some of the compounds of the formula (XVII) are novel, they can beprepared by processes known from the literature (Organikum 15th edition,p. 533, VEB Deutscher Verlag der Wissenschaften, Berlin 1977, cf., forexample, DE-196 49 665).

The compounds of the formula (XVII) are obtained, for example, byhydrolysing substituted phenylacetic esters of the formula (XVIII)

in which

-   W, X, Y, Z and R⁸ are each as defined above in the presence of an    acid (for example an inorganic acid such as hydrochloric acid) or a    base (for example an alkali metal hydroxide such as sodium hydroxide    or potassium hydroxide) and, if appropriate, a diluent (for example    an aqueous alcohol such as methanol or ethanol) at temperatures    between 0° C. and 150° C., preferably between 20° C. and 100° C.

Some of the compounds of the formula (XVIII) are novel, they can beprepared by processes known in principle.

The compounds of the formula (XVIII) are obtained, for example, byreacting substituted 1,1,1-trichloro-2-phenylethanes of the formula(XIX)

in which

-   W, X, Y and Z are each as defined above initially with alkoxides    (for example alkali metal alkoxides such as sodium methoxide or    sodium ethoxide) in the presence of a diluent (for example of the    alcohol derived from the alkoxide) at temperatures between 0° C. and    150° C., preferably between 20° C. and 120° C., and subsequently    reacting with an acid (preferably an inorganic acid, such as, for    example, sulphuric acid) at temperatures between −20° C. and 150°    C., preferably between 0° C. and 100° C. (cf. DE-3 314 249).

Some of the compounds of the formula (XIX) are novel, they can beprepared by processes known in principle.

The compounds of the formula (XIX) are obtained, for example, whenanilines of the formula (XX)

in which

-   W, X, Y and Z are each as defined above are reacted in the presence    of alkyl nitrite of the formula (XXI)    R¹³—ONO  (XXI)    in which-   R¹³ represents alkyl, preferably C₁–C₆-alkyl, in the presence of    copper(II) chloride and if appropriate in the presence of a diluent    (for example an aliphatic nitrile such as acetonitrile) at a    temperature of from −20° C. to 80° C., preferably of from 0° C. to    60° C., with vinylidene chloride (CH₂═CCl₂).

Some of the compounds of the formula (XX) are known. They can beprepared by processes known from the literature, for example byreduction of the corresponding nitro compounds or halogenation of theanilines or acetanilides and subsequent re-cleavage.

The compounds of the formula (XXI) are known compounds of organicchemistry. Copper(II) chloride and vinylidene chloride have been knownfor a long time and are commercially available.

The substituted cyclic aminocarboxylic acids of the formula (XVI) aregenerally obtainable by the Bucherer-Bergs synthesis or by the Streckersynthesis and are in each case obtained in these syntheses in differentisomer forms. Thus, under the conditions of the Bucherer-Bergssynthesis, the isomers (for simplicity called B below), in which theradicals R and the carboxyl group are equatorial are predominantlyobtained, while under the conditions of the Strecker synthesis theisomers (for simplicity called α below) in which the amino group and theradicals R are equatorial are pre-dominantly obtained.

The compounds of the formula (XIII) and (XVI) are novel. They can beprepared by known processes (see, for example, Compagnon, Ann. Chim.(Paris) [14] 5, p. 11–22, 23–27 (1970), L. Munday, J. Chem. Soc. 4372(1961); J. T. Eward, C. Jitrangeri, Can. J. Chem. 53, 3339 (1975)).

Furthermore, the starting materials of the formula (II)

in which

-   A, B, W, X, Y, Z and R⁸ are each as defined above, used in the above    process (A) can be prepared when aminonitriles of the formula (XXII)

in which

-   A and B are each as defined above, are reacted with substituted    phenylacetyl halides of the formula (XIV)

in which

-   W, X, Y, Z and Hal are each as defined above to give compounds of    the formula (XXIII)

in which

-   A, B, W, X, Y and Z are each as defined above and these are    subsequently subjected to acid alcoholysis.

The compounds of the formula (XXIII) are also novel. The compounds ofthe formula (XXII) are also novel.

The acyl halides of the formula (III), carboxylic anhydrides of theformula (IV), chloroformic esters or chloroformic thioesters of theformula (V), chloromonothioformic esters or chlorodithioformic esters ofthe formula (VI), sulphonyl chlorides of the formula (VII), phosphoruscompounds of the formula (VIII) and metal hydroxides, metal alkoxides oramines of the formula (IX) and (X) and isocyanates of the formula (XI)and carbamoyl chlorides of the formula (XII) furthermore required asstarting materials for carrying out the processes (B), (C), (D), (E),(F), (G) and (H) according to the invention are generally knowncompounds of organic or inorganic chemistry.

The compounds of the formulae (XIV), (XVII), (XVIII), (XIX) and (XX) arefurthermore known from the patent applications cited at the outsetand/or can be prepared by the methods given therein (cf. also DE-196 49665 and the Applicant's German Patent Application having file reference19613171.5 dated Feb. 4, 1996, which has not yet been laid open).

The process (A) is characterized in that compounds of the formula (II),in which A, B, W, X, Y, Z and R⁸ are each as defined above are subjectedto an intramolecular condensation in the presence of a diluent and inthe presence of a base.

Suitable diluents for use in the process (A) according to the inventionare all organic solvents which are inert towards the reactants.Preference is given to using hydrocarbons, such as toluene and xylene,furthermore ethers, such as dibutyl ether, tetrahydrofuran, dioxane,glycol dimethyl ether and diglycol dimethyl ether, moreover polarsolvents, such as dimethyl sulphoxide, sulpholane, dimethylformamide andN-methyl-pyrrolidone, and also alcohols such as methanol, ethanol,propanol, isopropanol, butanol, isobutanol and tert-butanol.

Suitable bases (deprotonating agents) for use in the practice of theprocess (A) according to the invention are all customary protonacceptors. Preference is given to using alkali metal and alkaline earthmetal oxides, hydroxides and carbonates, such as sodium hydroxide,potassium hydroxide, magnesium oxide, calcium oxide, sodium carbonate,potassium carbonate and calcium carbonate, which may also be used in thepresence of phase transfer catalysts, such as, for example,triethylbenzylammonium chloride, tetrabutylammonium bromide, Adogen 464(=methyltrialkyl(C₈–C₁₀)ammonium chloride) or TDA 1(=tris-(methoxyethoxyethyl)amine). It is also possible to use alkalimetals such as sodium or potassium.

Furthermore, it is possible to use alkali metal and alkaline earth metalamides and hydrides, such as sodium amide, sodium hydride and calciumhydride, and moreover also alkali metal alkoxides, such as sodiummethoxide, sodium ethoxide and potassium tert-butoxide.

When carrying out the process (A) according to the invention, thereaction temperature can be varied within a relatively wide range. Ingeneral, the reaction is carried out at temperatures between −75° C. and200° C., preferably between −50° C. and 150° C.

The process (A) according to the invention is generally carried outunder atmospheric pressure.

When carrying out the process (A) according to the invention, thereaction component of the formula (II) and the deprotonating base aregenerally employed in equimolar to about doubly-equimolar amounts.However, it is also possible to use one component or the other in arelatively large excess (up to 3 mol).

The process (B_(α)) is characterized in that compounds of the formula(I-a) are reacted with carbonyl halides of the formula (III), ifappropriate in the presence of a diluent and if appropriate in thepresence of an acid binder.

Suitable diluents for use in the process (B_(α)) according to theinvention are all solvents which are inert towards the acyl halides.Preference is given to using hydrocarbons, such as benzine, benzene,toluene, xylene and tetralin, furthermore halogenated hydrocarbons, suchas methylene chloride, chloroform, carbon tetrachloride, chlorobenzeneand o-dichlorobenzene, furthermore ketones, such as acetone and methylisopropyl ketone, additionally ethers, such as diethyl ether,tetrahydrofuran and dioxane, furthermore, carboxylic esters, such asethyl acetate, and also strongly polar solvents, such asdimethylformamide, dimethyl sulphoxide and sulpholane. The hydrolyticstability of the acyl halide permitting, the reaction can also becarried out in the presence of water.

Suitable acid binders for the reaction according to the process (B_(α))according to the invention are all customary acid acceptors. Preferenceis given to using tertiary amines, such as triethylamine, pyridine,diazabicyclooctane (DABCO), diazabicycloundecene (DBU),diazabicyclononene (DBN), Hunig base and N,N-dimethyl-aniline,furthermore alkaline earth metal oxides, such as magnesium oxide andcalcium oxide, and also alkali metal and alkaline earth metalcarbonates, such as sodium carbonate, potassium carbonate and calciumcarbonate and also alkali metal hydroxides such as sodium hydroxide andpotassium hydroxide.

The reaction temperature of the process (B_(α)) according to theinvention can be varied within a relatively wide range. In general, thereaction is carried out at temperatures between −20° C. and +150° C.,preferably between 0° C. and 100° C.

When carrying out the process (B_(α)) according to the invention, thestarting materials of the formula (I-a) and the carbonyl halide of theformula (III) are generally each employed in approximately equivalentamounts. However, it is also possible to employ a relatively largeexcess (up to 5 mol) of the carbonyl halide. Work-up is carried out bycustomary methods.

The process (Bβ) is characterized in that compounds of the formula (I-a)are reacted with carboxylic anydrides of the formula (IV), ifappropriate in the presence of a diluent and if appropriate in thepresence of an acid binder.

Suitable diluents for use in the process (Bβ) according to the inventionare preferably those diluents which are also preferred when acyl halidesare used. Additionally, a carboxylic anhydride employed in excess canalso simultaneously act as diluent.

The acid binders which are added in the process (Bβ), if appropriate,are preferably those acid binders which are also preferred when acylhalides are used.

The reaction temperature in the process (Bβ) according to the inventioncan be varied within a relatively wide range. In general, the reactionis carried out at temperatures between −20° C. and +150° C., preferablybetween 0° C. and 100° C.

When carrying out the process (Bβ) according to the invention, thestarting materials of the formula (I-a) and the carboxylic anhydride ofthe formula (IV) are generally each employed in approximately equivalentamounts. However, it is also possible to employ a relatively largeexcess (up to 5 mol) of the carboxylic anhydride. Work-up is carried outby customary methods.

In general, diluent and excess carboxylic anhydride and also thecarboxylic acid formed are removed by distillation or by washing with anorganic solvent or with water.

The process (C) is characterized in that compounds of the formula (I-a)are reacted with chloroformic esters or chloroformic thiol esters of theformula (V), if appropriate in the presence of a diluent and ifappropriate in the presence of an acid binder.

Acid binders which are suitable for the process (C) according to theinvention are all customary acid acceptors. Preference is given to usingtertiary amines, such as triethylamine, pyridine, DABCO, DBU, DBN, Hünigbase and N,N-dimethyl-aniline, furthermore alkaline earth metal oxides,such as magnesium oxide and calcium oxide, moreover alkali metal andalkaline earth metal carbonates, such as sodium carbonate, potassiumcarbonate and calcium carbonate, and also alkali metal hydroxides suchas sodium hydroxide and potassium hydroxide.

Suitable diluents for use in the process (C) according to the inventionare all solvents which are inert towards the chloroformic esters orchloroformic thiol esters. Preference is given to using hydrocarbons,such as benzine, benzene, toluene, xylene and tetralin, furthermore,halogenated hydrocarbons, such as methylene chloride, chloroform, carbontetrachloride, chlorobenzene and o-dichlorobenzene, furthermore ketones,such as acetone and methyl isopropyl ketone, moreover ethers, such asdiethyl ether, tetrahydrofuran and dioxane, furthermore carboxylicesters, such as ethyl acetate, additionally nitrites such asacetonitrile and also strongly polar solvents, such asdimethylformamide, dimethyl sulphoxide and sulpholane.

When carrying out the process (C) according to the invention, thereaction temperature can be varied within a relatively wide range. Ingeneral, the reaction temperature is between −20° C. and +100° C.,preferably between 0° C. and 50° C.

The process (C) according to the invention is generally carried outunder atmospheric pressure.

When carrying out the process (C) according to the invention, thestarting materials of the formula (I-a) and the appropriate chloroformicester or chloroformic thiol ester of the formula (VII) are generallyeach employed in approximately equivalent amounts. However, it is alsopossible to employ one component or the other in a relatively largeexcess (up to 2 mol). Work-up is carried out by customary methods. Ingeneral, precipitated salts are removed and the reaction mixture whichremains is concentrated by removing the diluent under reduced pressure.

The process (D) according to the invention is characterized in thatcompounds of the formula (I-a) are reacted with compounds of the formula(VI) in the presence of a diluent and, if appropriate, in the presenceof an acid binder.

In the preparation process (D), approximately 1 mol ofchloromonothioformic ester or chlorodithioformic ester of the formula(VI) per mole of starting material of the formula (I-a) is reacted at 0to 120° C., preferably at 20 to 60° C.

Diluents which may be added, if appropriate, are all inert polar organicsolvents, such as ethers, amides, sulphones, sulphoxides, and alsohalogenoalkanes.

Preference is given to using dimethyl sulphoxide, tetrahydrofuran,dimethylformamide, ethyl acetate or methylene chloride.

If, in a preferred embodiment, the enolate salt of the compounds of theformula (I-a) is prepared by addition of strong deprotonating agentssuch as, for example, sodium hydride or potassium tert-butoxide, theaddition of acid binders can be dispensed with.

Suitable bases for use in the process (D) are all customary protonacceptors. Preference is given to using alkali metal hydrides, alkalimetal alkoxides, alkali metal or alkaline earth metal carbonates orbicarbonates or nitrogen bases. Examples include sodium hydride, sodiummethoxide, sodium hydroxide, calcium hydroxide, potassium carbonate,sodium bicarbonate, triethylamine, dibenzylamine, diisopropylamine,pyridine, quinoline, diazabicyclooctane (DABCO), diazabicyclononene(DBN) and diazabicycloundecene (DBU).

The reaction can be carried out under atmospheric pressure or underelevated pressure and is preferably carried out under atmosphericpressure. Work-up is carried out by customary methods.

The process (E) according to the invention is characterized in thatcompounds of the formula (I-a) are in each case reacted with sulphonylchlorides of the formula (VII), if appropriate in the presence of adiluent and if appropriate in the presence of an acid binder.

In the preparation process (E), approximately 1 mol of sulphonylchloride of the formula (IX) per mole of starting material of theformula (I-a) is reacted at −20 to 150° C., preferably at 0 to 70° C.

The process (E) is preferably carried out in the presence of a diluent.

Suitable diluents are all inert polar organic solvents such as ethers,amides, ketones, carboxylic esters, nitrites, sulphones, sulphoxides orhalogenated hydrocarbons such as methylene chloride.

Preference is given to using dimethyl sulphoxide, tetrahydrofuran,dimethylformamide, ethyl acetate, methylene chloride.

If, in a preferred embodiment, the enolate salt of the compounds of theformula (I-a) is prepared by addition of strong deprotonating agents(such as, for example, sodium hydride or potassium tert-butoxide), theaddition of acid binders can be dispensed with.

If acid binders are used, then customary inorganic or organic bases aresuitable, examples being sodium hydroxide, sodium carbonate, potassiumcarbonate, pyridine and triethylamine.

The reaction can be carried out under atmospheric pressure or underelevated pressure and is preferably carried out under atmosphericpressure. Work-up is carried out by customary methods.

The process (F) according to the invention is characterized in thatcompounds of the formula (I-a) are in each case reacted with phosphoruscompounds of the formula (VIII), if appropriate in the presence of adiluent and if appropriate in the presence of an acid binder.

In the preparation process (F), 1 to 2, preferably 1 to 1.3, mol of thephosphorus compound of the formula (VIII) are reacted per mole of thecompounds of the formula (I-a) at temperatures between −40° C. and 150°C., preferably between −10 and 110° C., in order to obtain compounds ofthe formula (I-e).

The process (F) is preferably carried out in the presence of a diluent.

Suitable diluents are all inert, polar organic solvents such as ethers,carboxylic esters, halogenated hydrocarbons, ketones, amides, nitrites,sulphones, sulphoxides, etc.

Preference is given to using acetonitrile, dimethyl sulphoxide,tetrahydrofuran, dimethylformamide, methylene chloride.

Acid binders which are added, if appropriate, are customary inorganic ororganic bases, such as hydroxides, carbonates or amines. Examplesinclude sodium hydroxide, sodium carbonate, potassium carbonate,pyridine and triethylamine.

The reaction can be carried out under atmospheric pressure or underelevated pressure and is preferably carried out under atmosphericpressure. Work-up is carried out according to customary methods oforganic chemistry. The end products are preferably purified bycrystallization, chromatographic purification or by so-called “incipientdistillation”, i.e. removal of the volatile components under reducedpressure.

The process (G) is characterized in that compounds of the formula (I-a)are in each case reacted with metal hydroxides or metal alkoxides of theformula (IX) or amines of the formula (X), if appropriate in thepresence of a diluent.

Diluents which are preferred for use in the process (G) according to theinvention are ethers such as tetrahydrofuran, dioxane, diethyl ether, orelse alcohols such as methanol, ethanol, isopropanol, but also water.The process (G) according to the invention is generally carried outunder atmospheric pressure. The reaction temperature is generallybetween −20° C. and 100° C., preferably between 0° C. and 50° C.

The process (H) according to the invention is characterized in thatcompounds of the formula (I-a) are in each case reacted with (Hα)compounds of the formula (XI), if appropriate in the presence of adiluent and if appropriate in the presence of a catalyst, or (Hβ) withcompounds of the formula (XII), if appropriate in the presence of adiluent and if appropriate in the presence of an acid binder.

In the preparation process (Hα), approximately 1 mol of isocyanate ofthe formula (XI) is reacted per mole of starting material of the formula(I-a) at 0 to 100° C., preferably at 20 to 50° C.

The process (Hα) is preferably carried out in the presence of a diluent.

Suitable diluents are all inert organic solvents, such as aromatichydrocarbons, halogenated hydrocarbons, ethers, amides, nitriles,sulphones or sulphoxides.

If appropriate, catalysts may be added to accelerate the reaction.Catalysts which can be employed very advantageously are organotincompounds, such as, for example, dibutyltin dilaurate.

The process is preferably carried out under atmospheric pressure.

In the preparation process (Hβ), approximately 1 mol of carbamoylchloride of the formula (XIII) is reacted per mole of starting materialof the formula (I-a) at 0 to 150° C., preferably at 20 to 70° C.

Diluents which may be added, if appropriate, are all inert polar organicsolvents such as ethers, carboxylic esters, nitriles, ketones, amides,sulphones, sulphoxides or halogenated hydrocarbons.

Preference is given to using dimethyl sulphoxide, tetrahydrofuran,dimethylformamide or methylene chloride.

If, in a preferred embodiment, the enolate salt of the compounds of theformula (I-a) is prepared by addition of strong deprotonating agents(such as, for example, sodium hydride or potassium tert-butoxide), theaddition of acid binders can be dispensed with.

If acid binders are employed, then customary inorganic or organic basesare suitable, examples including sodium hydroxide, sodium carbonate,potassium carbonate, triethylamine or pyridine.

The reaction can be carried out under atmospheric pressure or underelevated pressure and is preferably carried out under atmosphericpressure. Work-up is carried out by customary methods.

The active compounds are suitable for controlling animal pests,preferably arthropods and nematodes, in particular insects andarachnids, which are encountered in agriculture, in forests, in theprotection of stored products and of materials, and in the hygienefield. They are active against normally sensitive and resistant speciesand against all or some stages of development. The abovementioned pestsinclude:

From the order of the Isopoda, for example, Oniscus asellus,Armadillidium vulgare and Porcellio scaber.

From the order of the Diplopoda, for example, Blaniulus guttulatus.

From the order of the Chilopoda, for example, Geophilus carpophagus andScutigera spec.

From the order of the Symphyla, for example, Scutigerella immaculata.

From the order of the Thysanura, for example, Lepisma saccharina.

From the order of the Collembola, for example, Onychiurus armatus.

From the order of the Orthoptera, for example, Blatta orientalis,Periplaneta americana, Leucophaea maderae, Blattella germanica, Achetadomesticus, Gryllotalpa spp., Locusta migratoria migratorioides,Melanoplus differentialis and Schistocerca gregaria.

From the order of the Dermaptera, for example, Forficula auricularia.

From the order of the Isoptera, for example, Reticulitermes spp.

From the order of the Anoplura, for example, Phylloxera vastatrix,Pemphigus spp., Pediculus humanus corporis, Haematopinus spp. andLinognathus spp.

From the order of the Mallophaga, for example, Trichodectes spp. andDamalinea spp.

From the order of the Thysanoptera, for example, Frankliniellaoccidentalis, Hercinothrips femoralis, Thrips palmi, and Thrips tabaci.

From the order of the Heteroptera, for example, Eurygaster spp.,Dysdercus intermedius, Piesma quadrata, Cimex lectularius, Rhodniusprolixus and Triatoma spp.

From the order of the Homoptera, for example, Aleurodes brassicae,Bemisia tabaci, Trialeurodes vaporariorun, Aphis gossypii, Brevicorynebrassicae, Cryptomyzus ribis, Aphis fabae, Doralis pomi, Eriosomalanigerum, Hyalopterus arundinis, Macrosiphum avenae, Myzus spp.,Phorodon humuli, Rhopalosiphum padi, Empoasca spp., Euscelis bilobatus,Nephotettix cincticeps, Lecanium corni, Saissetia oleae, Laodelphaxstriatellus, Nilaparvata lugens, Aonidiella aurantii, Aspidiotushederae, Pseudococcus spp. and Psylla spp.

From the order of the Lepidoptera, for example, Pectinophoragossypiella, Bupalus piniarius, Cheimatobia brumata, Lithocolletisblancardella, Hyponomeuta padella, Plutella maculipennis, Malacosomaneustria, Euproctis chrysorrhoea, Lymantria spp. Bucculatrixthurberiella, Phyllocnistis citrella, Agrotis spp., Euxoa spp., Feltiaspp., Earias insulana, Heliothis spp., Spodoptera exigua, Mamestrabrassicae, Panolis flammea, Prodenia litura, Spodoptera spp.,Trichoplusia ni, Carpocapsa pomonella. Pieris spp., Chilo spp., Pyraustanubilalis, Ephestia kuehniella, Galleria mellonella, Tineolabisselliella, Tinea pellionella, Hofmannophila pseudospretella, Cacoeciapodana, Capua reticulana, Choristoneura fumiferana, Clysia ambiguella,Homona magnanima and Tortrix viridana.

From the order of the Coleoptera, for example, Anobium punctatum,Rhizopertha dominica, Acanthoscelides obtectus, Acanthoscelidesobtectus, Hylotrupes bajulus, Agelastica alni, Leptinotarsadecemlineata, Phaedon cochleariae, Diabrotica spp., Psylliodeschrysocephala, Epilachna varivestis, Atomaria spp., Oryzaephilussurinamensis, Anthonomus spp., Sitophilus spp., Otiorrhynchus sulcatus,Cosmopolites sordidus, Ceuthorrhynchus assimilis, Hypera postica,Dermestes spp., Trogoderma spp., Anthrenus spp., Attagenus spp., Lyctusspp., Meligethes aeneus, Ptinus spp., Niptus hololeucus, Gibbiumpsylloides, Tribolium spp., Tenebrio molitor, Agriotes spp., Cono derusspp., Melolontha melolontha, Amphimallon solsti tialis and Costelytrazealandica.

From the order of the Hymenoptera, for example, Diprion spp., Hoplocampaspp., Lasius spp., Monomorium pharaonis and Vespa spp.

From the order of the Diptera, for example, Aedes spp., Anopheles spp.,Culex spp., Drosophila melanogaster, Musca spp., Fannia spp., Calliphoraerythrocephala, Lucilia spp., Chrysomyia spp., Cuterebra spp.,Gastrophilus spp., Hyppobosca spp., Liriomyza spp., Stomoxys spp.,Oestrus spp., Hypoderma spp., Tabanus spp., Tannia spp., Bibiohortulanus, Oscinella frit, Phorbia spp., Pegomyia hyoscyami, Ceratitiscapitata, Dacus oleae and Tipula paludosa.

From the order of the Siphonaptera, for example, Xenopsylla cheopis andCeratophyllus spp.

From the order of the Arachnida, for example, Scorpio maurus andLatrodectus mactans.

From the order of the Acarina, for example, Acarus siro, Argas spp.,Ornithodoros spp., Dermanyssus gallinae, Eriophyes ribis, Phyllocoptrutaoleivora, Boophilus spp., Rhipicephalus spp., Amblyomma spp., Hyalommaspp., Ixodes spp., Psoroptes spp., Chorioptes spp., Sarcoptes spp.,Tarsonemus spp., Bryobia praetiosa, Panonychus spp. and Tetranychus spp.

The active compounds according to the invention have high insecticidaland acaricidal activity after foliar and soil application.

They can be employed particularly successfully against insects which areharmful to plants, such as, for example, against the larvae of themustard beetle (Phaedon cochleariae), against the larvae of the ricegreen leafhopper (Nephotettix cincticeps) and against the larvae of thegreen peach aphid (Myzus persicae).

The active compounds according to the invention can furthermore be usedas defoliants, desiccants, haulm killers and, especially, asweed-killers. By weeds, in the broadest sense, there are to beunderstood all plants which grow in locations where they are undesired.Whether the substances according to the invention act as total orselective herbicides depends essentially on the amount used.

The dosages of the active compounds according to the invention necessaryfor controlling weeds are between 0.001 and 10 kg/ha, preferably between0.005 and 5 kg/ha.

The active compounds according to the invention can be used, forexample, in connection with the following plants:

Dicotyledonous weeds of the genera: Sinapis, Lepidium, Galium,Stellaria, Matricaria, Anthemis, Galinsoga, Chenopodium, Urtica,Senecio, Amaranthus, Portulaca, Xanthium, Convolvulus, Ipomoea,Polygonum, Sesbania, Ambrosia, Cirsium, Carduus, Sonchus, Solanum,Rorippa, Rotola, Lindemia, Lamium, Veronica, Abutilon, Emex, Datura,Viola, Galeopsis, Papaver, Centaurea, Trifolium, Ranunculus andTaraxacum.

Dicotyledonous crops of the genera: Gossypium, Glycine, Beta, Daucus,Phaseolus, Pisum, Solanum, Linum, Ipomoea, Vicia, Nicotiana,Lycopersicon, Arachis, Brassica, Lactuca, Cucumis and Cucurbita.

Monocotyledonous weeds of the genera: Echinochloa, Setaria, Panicum,Digitaria, Phleum, Poa, Festuca, Eleusine, Brachiaria, Lolium, Bromus,Avena, Cyperus, Sorghum, Agropyron, Cycnodon, Monochoria, Fimbristylis,Sagittaria, Eleocharis, Scirpus, Paspalum, Ischaemum, Sphenoclea,Dactyloctenium, Agrostis, Alopecurus and Apera.

Monocotyledonous crops of the genera: Oryza, Zea, Triticum, Hordeum,Avena, Secale, Sorghum, Panicum, Saccharum, Ananas, Asparagus andAllium.

However, the use of the active compounds according to the invention isin no way restricted to these genera, but also extends in the samemanner to other plants.

The compounds are suitable, depending on the concentration, for thetotal controlling of weeds, for example on industrial terrain and railtracks, and on paths and squares with or without tree plantings.Equally, the compounds can be employed for controlling weeds inperennial cultures, for example afforestations, decorative treeplantings, orchards, vineyards, citrus groves, nut orchards, bananaplantations, coffee plantations, tea plantations, rubber plantations,oil palm plantations, cocoa plantations, soft fruit plantings and hopfields, on ornamental and sports lawns and meadow areas and for theselective controlling of weeds in annual cultures.

The active compounds according to the invention are particularlysuitable for selectively controlling monocotyledonous weeds indicotyledonous crops by the pre- and post-emergence method. For example,they can be employed very successfully for controlling harmful grassesin cotton or sugar beet.

The active compounds can be converted into the customary formulations,such as solutions, emulsions, wettable powders, suspensions, powders,dusting agents, pastes, soluble powders, granules, suspension-emulsionconcentrates, natural and synthetic materials impregnated with activecompound, and very fine capsules in polymeric substances.

These formulations are produced in a known manner, for example by mixingthe active compounds with extenders, that is liquid solvents and/orsolid carriers, optionally with the use of surface-active agents, thatis emulsifying agents and/or dispersing agents and/or foam-formingagents.

If the extender used is water, it is also possible to employ, forexample, organic solvents as auxiliary solvents. Suitable liquidsolvents are essentially: aromatics, such as xylene, toluene oralkylnaphthalenes, chlorinated aromatics and chlorinated aliphatichydrocarbons, such as chlorobenzenes, chloroethylenes or methylenechloride, aliphatic hydrocarbons, such as cyclohexane or paraffins, forexample petroleum fractions, mineral and vegetable oils, alcohols, suchas butanol or glycol as well as their ethers and esters, ketones, suchas acetone, methyl ethyl ketone, methyl isobutyl ketone orcyclohexanone, strongly polar solvents, such as dimethylformamide anddimethyl sulphoxide, and also water.

As solid carriers there are suitable:

for example, ammonium salts and ground natural minerals, such askaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite ordiatomaceous earth, and ground synthetic minerals, such as highlydisperse silica, alumina and silicates; as solid carriers for granulesthere are suitable: for example, crushed and fractionated natural rockssuch as calcite, marble, pumice, sepiolite and dolomite, and alsosynthetic granules of inorganic and organic meals, and granules oforganic material such as sawdust, coconut shells, maize cobs and tobaccostalks; as emulsifying and/or foam-forming agents there are suitable:for example, non-ionic and anionic emulsifiers, such as polyoxyethylenefatty acid esters, polyoxyethylene fatty alcohol ethers, for examplealkylaryl polyglycol ethers, alkyl sulphonates, alkyl sulphates, arylsulphonates and also protein hydrolysates; as dispersing agents thereare suitable: for example, lignin-sulphite waste liquors andmethylcellulose.

Tackifiers such as carboxymethylcellulose and natural and syntheticpolymers in the form of powders, granules or latexes, such as gumarabic, polyvinyl alcohol and polyvinyl acetate, and also naturalphospholipids, such as cephalins and lecithins, and syntheticphospholipids, can be used in the formulations. Other possible additivesare mineral and vegetable oils.

It is possible to use colorants such as inorganic pigments, for exampleiron oxide, titanium oxide and Prussian Blue, and organic dyestuffs,such as alizarin dyestuffs, azo dyestuffs and metal phthalocyaninedyestuffs, and trace nutrients such as salts of iron, manganese, boron,copper, cobalt, molybdenum and zinc.

The formulations in general contain between 0.1 and 95% by weight ofactive compound, preferably between 0.5 and 90%, and additionallypreferably extenders and/or surfactants.

The active compound according to the invention can be present in itscommercially available formulations and in the use forms prepared fromthese formulations as a mixture with other active compounds, such asinsecticides, baits, sterilizing agents, acaricides, nematicides,fungicides, growth-regulating substances or herbicides. The insecticidesinclude, for example, phosphoric acid esters, carbamates, carboxylicacid esters, chlorinated hydrocarbons, phenylureas, substances producedby microorganisms, and the like.

Particularly favourable mixing partners are, for example, the following:

Fungicides:

2-aminobutane; 2-anilino-4-methyl-6-cyclopropyl-pyrimidine;2′,6′-dibromo-2-methyl-4′-trifluoromethoxy-4′-trifluoro-methyl-1,3-thiazole-5-carboxanilide;2,6-dichloro-N-(4-trifluoromethylbenzyl)-benzamide;(E)-2-methoxyimino-N-methyl-2-(2-phenoxy-phenyl)-acetamide;8-hydroxyquinoline sulphate; methyl(E)-2-{2-[6-(2-cyanophenoxy)-pyrimidin-4-yloxy]-phenyl}-3-methoxyacrylate;methyl (E)-methoximino[alpha-(o-tolyloxy)-o-tolyl]acetate;2-phenylphenol (OPP), aldimorph, ampropylfos, anilazine, azaconazole,benalaxyl, benodanil, benomyl, binapacryl, biphenyl, bitertanol,blasticidin-S, bromuconazole, bupirimate, buthiobate, calciumpolysulphide, captafol, captan, carbendazim, carboxin, quinomethionate,chloroneb, chloropicrin, chlorothalonil, chlozolinate, cufraneb,cymoxanil, cyproconazole, cyprofuram, dichlorophen, diclobutrazol,diclofluanid, diclomezin, dicloran, diethofencarb, difenoconazole,dimethirimol, dimethomorph, diniconazole, dinocap, diphenylamine,dipyrithion, ditalimfos, dithianon, dodine, drazoxolon, edifenphos,epoxyconazole, ethirimol, etridiazole, fenarimol, fenbuconazole,fenfuram, fenitropan, fenpiclonil, fenpropidin, fenpropimorph, fentinacetate, fentin hydroxide, ferbam, ferimzone, fluazinam, fludioxonil,fluoromide, fluquinconazole, flusilazole, flusulfamide, flutolanil,flutriafol, folpet, fosetyl-aluminium, fthalide, fuberidazole,furalaxyl, furmecyclox, guazatine, hexachlorobenzene, hexaconazole,hymexazol, imazalil, imibenconazole, iminoctadine, iprobenfos (IBP),iprodione, isoprothiolane, kasugamycin, copper preparations such as:copper hydroxide, copper naphthenate, copper oxychloride, coppersulphate, copper oxide, oxine-copper and Bordeaux mixture, mancopper,mancozeb, maneb, mepanipyrim, mepronil, metalaxyl, metconazole,methasulfocarb, methfuroxam, metiram, metsulfovax, myclobutanil, nickeldimethyldithiocarbamate, nitrothal-isopropyl, nuarimol, ofurace,oxadixyl, oxamocarb, oxycarboxin, pefurazoate, penconazole, pencycuron,phosdiphen, phthalide, pimaricin, piperalin, polycarbamate, polyoxin,probenazole, prochloraz, procymidone, propamocarb, propiconazole,propineb, pyrazophos, pyrifenox, pyrimethanil, pyroquilon, quintozene(PCNB), sulphur and sulphur preparations, tebuconazole, tecloftalam,tecnazene, tetraconazole, thiabendazole, thicyofen, thiophanate-methyl,thiram, tolclophos-methyl, tolylfluanid, triadimefon, triadimenol,triazoxide, trichlamide, tricyclazole, tridemorph, triflumizole,triforine, triticonazole, validamycin A, vinclozolin, zineb, ziram

Bactericides:

bronopol, dichlorophen, nitrapyrin, nickel dimethyldithiocarbamate,kasugamycin, octhilinon, furancarboxylic acid, oxytetracyclin,probenazol, streptomycin, tecloftalam, copper sulphate and other copperpreparations.

Insecticides/Acaricides/Nematicides:

abamectin, AC 303 630, acephate, acrinathrin, alanycarb, aldicarb,alphamethrin, amitraz, avernectin, AZ 60541, azadirachtin, azinphos A,azinphos M, azocyclotin, Bacillus thuringiensis, bendiocarb,benfuracarb, bensultap, beta-cyfluthrin, bifenthrin, BPMC, brofenprox,bromophos A, bufencarb, buprofezin, butocarboxin, butylpyridaben,cadusafos, carbaryl, carbofuran, carbophenothion, carbosulfan, cartap,CGA 157 419, CGA 184 699, chloethocarb, chlorethoxyfos, chlorfenvinphos,chlorfluazuron, chlonnephos, chlorpyrifos, chlorpyrifos M,cis-resmethrin, clocythrin, clofentezine, cyanophos, cycloprothrin,cyfluthrin, cyhalothrin, cyhexatin, cypermethrin, cyromazine,deltamethrin, demeton-M, demeton-S, demeton-S-methyl, diafenthiuron,diazinon, dichlofenthion, dichlorvos, dicliphos, dicrotophos, diethion,diflubenzuron, dimethoate, dimethylvinphos, dioxathion, disulfoton,edifenphos, emamectin, esfenvalerate, ethiofencarb, ethion, ethofenprox,ethoprophos, etrimphos, fenamiphos, fenazaquin, fenbutatin oxide,fenitrothion, fenobucarb, fenothiocarb, fenoxycarb, fenpropathrin,fenpyrad, fenpyroximate, fenthion, fenvalerate, fipronil, fluazinam,flucycloxuron, flucythrinate, flufenoxuron, flufenprox, fluvalinate,fonophos, formothion, fosthiazate, fubfenprox, furathiocarb, HCH,heptenophos, hexaflumuron, hexythiazox, imidacloprid, iprobenfos,isazophos, isofenphos, isoprocarb, isoxathion, ivermectin,lambda-cyhalothrin, lufenuron, malathion, mecarbam, mevinphos,mesulfenphos, metaldehyde, methacrifos, methamidophos, methidathion,methiocarb, methomyl, metolcarb, milbemectin, monocrotophos, moxidectin,naled, NC 184, NI 25, nitenpyram, omethoate, oxamyl, oxydemethon M,oxydeprofos, parathion A, parathion M, permethrin, phenthoate, phorate,phosalone, phosmet, phosphamidon, phoxim, pirimicarb, pirimiphos M,primiphos A, profenofos, promecarb, propaphos, propoxur, prothiofos,prothoate, pymetrozin, pyrachlophos, pyridaphenthion, pyresmethrin,pyrethrum, pyridaben, pyrimidifen, pyriproxifen, quinalphos, RH 5992,salithion, sebufos, silafluofen, sulfotep, suiprofos, tebufenozid,tebufenpyrad, tebupirimiphos, teflubenzuron, tefluthrin, temephos,terbam, terbufos, tetrachlorvinphos, thiafenox, thiodicarb, thiofanox,thiomethon, thionazin, thuringiensin, tralomethrin, triarathen,triazophos, triazuron, trichlorfon, triflumuron, trimethacarb,vamidothion, XMC, xylylcarb, YI 5301/5302, zetamethrin.

Herbicides:

for example anilides, such as, for example, diflufenican and propanil;arylcarboxylic acids such as, for example, dichloropicolinic acid,dicamba and picloram; aryloxyalkanoic acids, such as, for example, 2,4D, 2,4 DB, 2,4 DP, fluroxypyr, MCPA, MCPP and triclopyr;aryloxy-phenoxy-alkanoic acid esters, such as, for example,diclofop-methyl, fenoxaprop-ethyl, fluazifop-butyl, haloxyfop-methyl andquizalofop-ethyl; azinones, such as, for example, chloridazon andnorflurazon; carbamates, such as, for example, chlorpropham,desmedipham, phenmedipham and propham; chloroacetanilides, such as, forexample, alachlor, acetochlor, butachlor, metazachlor, metolachlor,pretilachlor and propachlor; dinitroanilines, such as, for example,oryzalin, pendimethalin and trifluralin; diphenyl ethers, such as, forexample, acifluorfen, bifenox, fluoroglycofen, fomesafen, halosafen,lactofen and oxyfluorfen; ureas, such as, for example, chlortoluron,diuron, fluometuron, isoproturon, linuron and methabenzthiazuron;hydroxylamines, such as, for example, alloxydim, clethodim, cycloxydim,sethoxydim and tralkoxydim; imidazolinones, such as, for example,imazethapyr, imazamethabenz, imazapyr and imazaquin; nitriles, such as,for example, bromoxynil, dichlobenil and ioxynil; oxyacetamides, suchas, for example, mefenacet; sulfonylureas, such as, for example,amidosulfuron, bensulfuron-methyl, chlorimuronethyl, chlorsulfuron,cinosulfuron, metsulfuron-methyl, nicosulfuron, primisulfuron,pyrazosulfuron-ethyl, thifensulfiron-methyl, triasulfuron andtribenuron-methyl; thiocarbamates, such as, for example, butylate,cycloate, di-allate, EPTC, esprocarb, molinate, prosulfocarb,thiobencarb and tri-allate; triazines, such as, for example, atrazine,cyanazine, simazine, simetryn, terbutryn and terbutylazine; triazinones,such as, for example, hexazinone, metamitron and metribuzin; others,such as, for example, aminotriazole, benfuresate, bentazone,cinmethylin, clomazone, clopyralid, difenzoquat, dithiopyr,ethofumesate, fluorochloridone, glufosinate, glyphosate, isoxaben,pyridate, quinchlorac, quinmerac, sulphosate and tridiphane.

The active compound according to the invention can furthermore bepresent in its commercially available formulations and in the use forms,prepared from these formulations, as a mixture with synergists.Synergists are compounds which increase the action of the activecompounds without it being necessary for the synergist added to beactive itself.

The active compound content of the use forms prepared from thecommercially available formulations can vary within wide limits. Theactive compound concentration of the use forms can be from 0.0000001 to95% by weight of active compound, preferably between 0.0001 and 1% byweight.

The compounds are used in a customary manner appropriate for the useforms.

When used against hygiene pests and pests of stored products, the activecompound has outstanding residual action on wood and clay and astability to alkali on limed substrates.

The active compounds according to the invention have an action not onlyagainst plant and hygiene pests and pests of stored products, but alsoin the veterinary medicine sector against animal parasites(ectoparasites), such as hard ticks, soft ticks, mange mites, harvestmites, flies (biting and licking), parasitic fly larvae, lice, hairlice, bird lice and fleas. These parasites include:

From the order of the Anoplurida, for example, Haematopinus spp.,Linognathus spp., Pediculus spp., Phtirus spp. and Solenopotes spp.

From the order of the Mallophagida and the suborders Amblycerina andIschnocerina, for example, Trimenopon spp., Menopon spp., Trinoton spp.,Bovicola spp., Werneckiella spp., Lepikentron spp., Damalina spp.,Trichodectes spp., Felicola spp.

From the order of the Diptera and the suborders Nematocerina andBrachycerina, for example, Aedes spp., Anopheles spp., Culex spp.,Simulium spp., Eusimulium spp., Phlebotomus spp., Lutzomyia spp.,Culicoides spp., Chrysops spp., Hybomitra spp., Atylotus spp., Tabanusspp., Haematopota spp., Philipomyia spp., Braula spp. Musca spp.,Hydrotaea spp., Stomoxys spp., Haematobia spp., Morellia spp., Fanniaspp., Glossina spp., Calliphora spp., Lucilia spp., Chrysomyia spp.,Wohlfahrtia spp., Sarcophaga spp., Oestrus spp., Hypoderna spp.,Gasterophilus spp., Hippobosca spp., Lipoptena spp. and Melophagus spp.

From the order of the Siphonapterida, for example, Pulex spp.,Ctenocephalides spp., Xenopsylla spp. and Ceratophyllus spp.

From the order of the Heteropterida, for example, Cimex spp., Triatomaspp., Rhodnius spp. and Panstrongylus spp.

From the order of the Blattarida, for example, Blatta orientalis,Periplaneta americana, Blattela germanica and Supella spp.

From the sub-class of the Acaria (Acarida) and the orders of the Meta-and Mesostigmata, for example, Argas spp., Ornithodorus spp., Otabiusspp., Ixodes spp., Amblyomma spp., Boophilus spp., Dermacentor spp.,Haemaphysalis spp., Hyalomma spp., Rhipicephalus spp., Dernanyssus spp.,Raillietia spp., Pneumonyssus spp., Sternostoma spp. and Varroa spp.

From the order of the Actinedida (Prostigmata) and Acaridida(Astigmata), for example, Acarapis spp., Cheyletiella spp.,Omithocheyletia spp., Myobia spp., Psorergates spp., Demodex spp.,Trombicula spp., Listrophorus spp., Acarus spp., Tyrophagus spp.,Caloglyphus spp., Hypodectes spp., Pterolichus spp., Psoroptes spp.,Chorioptes spp., Otodectes spp., Sarcoptes spp., Notoedres spp.,Knemidocoptes spp., Cytodites spp. and Laminosioptes spp.

The active compounds of the formula (I) according to the invention arealso suitable for controlling arthropods which infest agriculturalproductive livestock such as, for example, cattle, sheep, goats, horses,pigs, donkeys, camels, buffalo, rabbits, chickens, turkeys, ducks, geeseand bees, other pets, such as, for example, dogs, cats, cage birds andaquarium fish, and also so-called test animals, such as, for example,hamsters, guinea pigs, rats and mice. By controlling these arthropods,mortality and reductions in productivity (for meat, milk, wool, hides,eggs, honey, etc.) should be diminished, so that more economic andsimpler animal husbandry is possible by use of the active compoundsaccording to the invention.

The active compounds according to the invention are used in theveterinary sector in a known manner by enteral administration in theform of, for example, tablets, capsules, potions, drenches, granules,pastes, boli, the feed-through process and suppositories, by parenteraladministration, such as, for example, by injections (intramuscular,subcutaneous, intravenous, intraperitoneal, etc.), implants, by nasaladministration, by dermal use in the form, for example, of dipping orbathing, spraying, pouring on and spotting on, washing and powdering,and also with the aid of moulded articles containing the activecompound, such as collars, ear marks, tail marks, limb bands, halters,marking devices, etc.

When used for livestock, poultry, pets and the like, the activecompounds of the formula (I) can be used as formulations (for examplepowders, emulsions, flowables) which comprise the active compounds in anamount of 1 to 80% by weight, directly or after 100 to 10,000-folddilution, or they can be used as a chemical bath.

It has furthermore been found that the compounds of the formula (I)according to the invention display a high insecticidal action againstinsects which destroy industrial materials.

The following insects may be mentioned as examples and preferred—butwithout being limiting:

Beetles, such as

Hylotrupes bajulus, Chlorophorus pilosis, Anobium punctatum, Xestobiumrufovillosum, Ptilinus pecticornis, Dendrobium pertinex, Emobius mollis,Priobium carpini, Lyctus brunneus, Lyctus africanus, Lyctus planicollis,Lyctus linearis, Lyctus pubescens, Trogoxylon aequale, Minthesrugicollis, Xyleborus spec., Tryptodendron spec, Apate monachus,Bostrychus capucins, Heterobostrychus brunneus, Sinoxylon spec. andDinoderus minutus.

Hymenopterons, such as

Sirex juvencus, Urocerus gigas, Urocerus gigas taignus and Urocerusaugur.

Termites, such as

Kalotermes flavicollis, Cryptotermes brevis, Heterotermes indicola,Reticulitermes flavipes, Reticulitermes santonensis, Reticulitermeslucifugus, Mastotermes darwiniensis, Zootermopsis nevadensis andCoptotermes formosanus.

Bristletails, such as

Lepisma saccharina.

Industrial materials in the present connection are to be understood asmeaning non-living materials, such as, preferably, plastics, adhesives,sizes, papers and cards, leather, wood and processed wood products, andlacquers and paints.

Materials to be protected from insect damage which are quiteparticularly preferred are wood and processed wood products.

Wood and processed wood products which can be protected by the agentsaccording to the invention or mixtures comprising these are to beunderstood as meaning, for example: building timber, wooden beams,railway sleepers, bridge components, boat gangplanks, wooden vehicles,crates, pallets, containers, telegraph poles, wood lagging, woodenwindows and doors, plywood, chipboards, joinery or wood products usedquite generally in house construction or building joinery.

The active compounds can be used as such or in the form of concentratesor generally customary formulations, such as powders, granules,solutions, suspensions, emulsions or pastes.

The formulations mentioned can be prepared in a manner known per se, forexample by mixing the active compounds with at least one solvent ordiluent, emulsifier, dispersing agent and/or binder or fixing agent,water repellant, optionally siccatives and UV stabilizers, and ifappropriate dyestuffs and pigments, and also other processingauxiliaries.

The insecticidal compositions or concentrates used for preservation ofwood and derived timber products comprise the active compound accordingto the invention in a concentration of 0.0001 to 95% by weight, inparticular 0.001 to 60% by weight.

The amount of composition or concentrate employed depends on the natureand the occurrence of the insects and on the medium. The optimum amountemployed for the use can in each case be determined by a series oftests. In general, however, it is sufficient to employ 0.0001 to 20% byweight, preferably 0.001 to 10% by weight, of the active compound basedon the material to be preserved.

The solvent and/or diluent used is an organochemical solvent or solventmixture and/or an oily or oil-like organochemical solvent or solventmixture of low volatility and/or a polar organochemical solvent orsolvent mixture and/or water and, if appropriate, an emulsifier and/orwetting agent.

The organochemical solvents employed are preferably oily or oil-likesolvents having an evaporation number above 35 and a flash point above30° C., preferably above 45° C. Corresponding mineral oils or aromaticfractions thereof or solvent mixtures containing mineral oil, preferablywhite spirit, petroleum and/or alkylbenzene, are used as suchwater-insoluble, oily and oil-like solvents of low volatility.

Mineral oils having a boiling range from 170 to 220° C., white spirithaving a boiling range from 170 to 220° C., spindle oil having a boilingrange from 250 to 350° C., petroleum or aromatics having a boiling rangefrom 160 to 280° C., terpentine oil and the like are advantageouslyemployed.

In a preferred embodiment, liquid aliphatic hydrocarbons having aboiling range from 180 to 210° C. or high-boiling mixtures of aromaticand aliphatic hydrocarbons having a boiling range from 180 to 220° C.and/or spindle oil and/or monochloronaphthalene, preferablymonochloronaphthalene, are employed.

The organic oily or oil-like solvents of low volatility having anevaporation number above 35 and a flash point above 30° C., preferablyabove 45° C., can be replaced in part by organochemical solvents of highor medium volatility, provided that the solvent mixture likewise has anevaporation number above 35 and a flash point above 30° C., preferablyabove 45° C., and that the insecticide/fungicide mixture is soluble orcan be emulsified in this solvent mixture.

According to a preferred embodiment, some of the organochemical solventor solvent mixture is replaced by an aliphatic polar organochemicalsolvent or solvent mixture. Aliphatic organochemical solvents containinghydroxyl and/or ester and/or ether groups, such as, for example, glycolethers, esters or the like, are preferably used.

Organochemical binders which are used within the context of the presentinvention are the synthetic resins and/or binding drying oils which arewater-dilutable and/or soluble or dispersible or emulsifiable in theorganochemical solvents employed and are known per se, in particularbinders consisting of or comprising an acrylate resin, a vinyl resin,for example polyvinyl acetate, polyester resin, polycondensation orpolyaddition resin, polyurethane resin, alkyd resin or modified alkydresin, phenolic resin, hydrocarbon resin, such as indene-coumarone resinor silicone resin, drying plant and/or drying oils and/or binders whichdry by physical means and are based on a naturally occurring and/orsynthetic resin.

The synthetic resin used as the binder can be employed in the form of anemulsion, dispersion or solution. Bitumen or bituminous substances canalso be used as binders in an amount of up to 10% by weight. Inaddition, dyestuffs, pigments, water-repellant agents, odour correctantsand inhibitors or corrosion prevention agents and the like which areknown per se can be employed.

Preferably, according to the invention, the composition or concentratecomprises at least one alkyd resin or modified alkyd resin and/or onedrying plant oil as an organochemical binder. Alkyd resins having an oilcontent of more than 45% by weight, preferably 50 to 68% by weight, arepreferably used according to the invention.

All or some of the binder mentioned can be replaced by a fixing agent(mixture) or a plasticizer (mixture). These additives are intended toprevent evaporation of the active compounds and crystallization orprecipitation They preferably replace 0.01 to 30% of the binder (basedon 100% of the binder employed).

The plasticizers originate from the chemical classes of phthalic acidesters, such as dibutyl, dioctyl or benzyl butyl phthalate, phosphoricacid esters, such as tributyl phosphate, adipic acid esters, such asdi-(2-ethylhexyl) adipate, stearates, such as butyl stearate or amylstearate, oleates, such as butyl oleate, glycerol ethers or highermolecular weight glycol ethers, glycerol esters and p-toluenesulphonicacid esters.

Fixing agents are based chemically on polyvinyl alkyl ethers, such as,for example, polyvinyl methyl ether, or ketones, such as benzophenone orethylenebenzophenone.

Water in particular is also a possible solvent or diluent, ifappropriate mixed with one or more of the abovementioned organochemicalsolvents or diluents, emulsifiers and dispersing agents.

Particularly effective wood preservation is achieved by impregnationprocesses on a large industrial scale, for example vacuum, double vacuumor pressure processes.

If appropriate, the ready-to-use compositions can also comprise otherinsecticides, and if appropriate also one or more fungicides.

Possible additional admixing partners are, preferably, the insecticidesand fungicides mentioned in WO 94/29 268. The compounds mentioned inthis document are an express constituent of the present application.

Especially preferred admixing partners can be insecticides, such aschlorpyriphos, phoxim, silafluofin, alphamethrin, cyfluthrin,cypermethrin, deltamethrin, permethrin, imidacloprid, NI-25,flufenoxuron, hexaflumuron and triflumuron, and fungicides, such asepoxyconazole, hexaconazole, azaconazole, propiconazole, tebuconazole,cyproconazole, metconazole, imazalil, dichlorfluanid, tolylfluanid,3-iodo-2-propinyl butylcarbamate, N-octyl-isothiazolin-3-one and4,5-dichloro-N-octylisothiazolin-3-one.

The preparation and the use of the active compounds according to theinvention can be seen from the following examples.

EXAMPLE (I-a-1)

At reflux temperature, 24.8 g of the compound of Example (II-2) in 150ml of anhydrous toluene are added dropwise to 18.4 g (0.16 mol) ofpotassium tert-butoxide in 63 ml of anhydrous tetrahydrofuran (THF), andthe mixture is stirred at reflux for another 1.5 hours. 240 ml of waterare then added, the phases are separated and the toluene phase isextracted with water. The combined aqueous phases are washed withtoluene and, at 10 to 20° C., acidified with approximately 26 ml ofconc. hydrochloric acid. The precipitated solid is filtered off withsuction, washed and dried. For purification, the product is stirred in amixture of methyl tert-butyl ether (MTB ether) and n-hexane.

Yield 15.6 g (69% of theory), m.p.: >220° C.

Similar to this method, and/or according to the general preparationprocedures, the following compounds of the formula (I-a) are obtained:

TABLE 2 (I-a)

Ex. m.p. No. W X Y Z A B ° C. isomer I-a-2 CH₃ CH₃ CH₃ H CH₃ H 195 αI-a-3 H CH₃ CH₃ H CH₃ H 164 α I-a-4 H CH₃ CH₃ H CH₃ H 196 β I-a-5 C₂H₅C₂H₅ CN H CH₃ H 242 β I-a-6 H Cl Cl H CH₃ H >220 β I-a-7 H Cl CH₃ H CH₃H 194 β I-a-8 Cl CH₃ Cl H CH₃ H >220 β I-a-9 Cl Cl CH₃ H CH₃ H 211 βI-a-10 CH₃ CH₃ CH₃ CH₃ CH₃ H >220 β I-a-11 H CH₃ Cl H CH₃ H >220 βI-a-12 CH₃ CH₃ CN H CH₃ H >220 β I-a-13 CH₃ CH₃ H Cl CH₃ H 210 β I-a-14H CH₃ CH₃ CH₃ CH₃ H >220 β I-a-15 H Cl Br H CH₃ H >220 β I-a-16 CH₃ CH₃Cl H CH₃ H 211 β I-a-17 CH₃ CN CH₃ H CH₃ H >220 β I-a-18 CH₃ CH₃ Br HCH₃ H >220 β I-a-19 Br CH₃ Cl H CH₃ H 210 β I-a-20 H CH₃ H CH₃ CH₃H >220 β I-a-21 Br Br C₂H₅ H CH₃ H >220 β I-a-22 H Cl C₂H₅ H CH₃ H >220β I-a-23 CH₃ CH₃ CH₃ H CH₃ CH₃ >220 α I-a-24 H CH₃ CH₃ H CH₃ CH₃ >220 αI-a-25 H Cl Cl CH₃ CH₃ H >240 β I-a-26 H Cl CH₃ Cl CH₃ H >236 β I-a-27 HCH₃ Cl CH₃ CH₃ H >227 β I-a-28 H Br CH₃ Br CH₃ H >240 β I-a-29 H CH₃ ClCl CH₃ H 206 β I-a-30 Br Br i-C₃H₇ H CH₃ H 233 β I-a-31 Cl Cl Cl H CH₃H >234 β

EXAMPLE (I-b-1)

2.52 mol (18 mmol) of triethylamine are added to 3.62 g of the compoundof Example (I-a-1) in 70 ml of anhydrous methylene chloride. At 0 to 10°C., 1.9 ml (18 mmol) of isobutyryl chloride in 5 ml of anhydrousmethylene chloride are added to this mixture, and stirring is continuedat room temperature until the reaction has ended. The mixture is thenwashed twice with 50 ml of 0.5 N NaOH each time, dried and concentrated.The residue is recrystallized from MTB ether/n-hexane.

Yield 1.6 g (35% of theory), m.p.: 209° C.

Similar to this method, and/or according to the general preparationprocedures, the following compounds of the formula (I-b) are obtained:

TABLE 3 (I-b)

Ex. m.p. iso- No. W X Y Z A B R¹ ° C. mer I-b-2 CH₃ CH₃ CH₃ H CH₃ H CH₃176 α I-b-3 CH₃ CH₃ CH₃ H CH₃ H i-C₃H₇ 187 α I-b-4 H CH₃ CH₃ H CH₃ Hi-C₃H₇ α⁽¹⁾ I-b-5 CH₃ CH₃ CH₃ H CH₃ H CH₃ 187 β I-b-6 H CH₃ CH₃ H CH₃ HCH₃ 181 β I-b-7 H CH₃ CH₃ H CH₃ H i-C₃H₇ 211 β I-b-8 H Cl CH₃ H CH₃ Hi-C₃H₇ 155 β I-b-9 Cl Cl CH₃ H CH₃ H i-C₃H₇ 178 β I-b-10 CH₃ Cl Cl H CH₃H i-C₃H₇ 204 β I-b-11 CH₃ CH₃ CH₃ CH₃ CH₃ H i-C₃H₇ >220 β I-b-12 CH₃ CH₃CN H CH₃ H i-C₃H₇ 214 β I-b-13 CH₃ CH₃ CN H CH₃ H t-C₄H₉—CH₂ >220 βI-b-14 H CH₃ CH₃ CH₃ CH₃ H i-C₃H₇ 210 β I-b-15 H Cl Br H CH₃ H i-C₃H₇170 β I-b-16 H Cl Br H CH₃ H t-C₄H₉—CH₂ 194 β I-b-17 H CH₃ Cl H CH₃ Hi-C₃H₇ 178 β I-b-18 CH₃ CN CH₃ H CH₃ H i-C₃H₇ 214 β I-b-19 CH₃ CN CH₃ HCH₃ H t-C₄H₉—CH₂ >220 β I-b-20 CH₃ CH₃ Br H CH₃ H i-C₃H₇ >220 β I-b-21CH₃ CH₃ Br H CH₃ H t-C₄H₉—CH₂ >220 β I-b-22 H Cl C₂H₅ H CH₃ H i-C₃H₇ 179β I-b-23 H Cl C₂H₅ H CH₃ H

152 β I-b-24 H CH₃ CH₃ CH₃ CH₃ H

170 β I-b-25 CH₃ CH₃ Cl H CH₃ H i-C₃H₇ 160 β I-b-26 CH₃ CH₃ Cl H CH₃ Hs-C₄H₉ 200 β I-b-27 H CH₃ H CH₃ CH₃ H i-C₃H₇ 193 β I-b-28 CH₃ CH₃ CH₃ HCH₃ CH₃ i-C₃H₇ 191 α I-b-29 H Cl CH₃ Cl CH₃ H i-C₃H₇ 231 β I-b-30 H CH₃Cl CH₃ CH₃ H i-C₃H₇ 210 β I-b-31 H Br CH₃ Br CH₃ H i-C₃H₇ 214– β 216I-b-32 H Cl Cl CH₃ CH₃ H i-C₃H₇ 202– β 205 I-b-33 Br Br C₂H₅ H CH₃ Hi-C₃H₇ 217 β I-b-34 CH₃ CH₃ Cl H CH₃ H (CH₃)₂C═CH >248 β I-b-35 Cl Cl ClH CH₃ H i-C₃H₇ 207 β I-b-36 Br Br i-C₃H₇ H CH₃ H i-C₃H₇ 213 β ⁽¹⁾¹H-NMR(200 MHz, CDCl₃): δ = 1.0–1.05 (4s, 6H, CH(CH₃)₂), 2.25, 2.28 (25, 6H,ArCH ³ ).

EXAMPLE (I-c-1)

At 0 to 10° C., 1.2 ml (12 mmol) of ethyl chloroformate in 5 ml ofanhydrous methylene chloride are added dropwise to 3.62 g of thecompound of Example (I-a-1) and 1.7 ml (12 mmol) of triethylamine in 70ml of anhydrous methylene chloride, and the mixture is stirred at roomtemperature until the reaction has ended. The mixture is then washed twotimes with 50 ml of 0.5 N NaOH each time, dried and concentrated and theresidue is recrystallized from MTB ether/n-hexane.

Yield 2.70 g (60% of theory), m.p.: 217° C.

Similar to this method, and/or according to the general preparationprocedures, the following compounds of the formula (I-c) are obtained:

TABLE 4 (I-c)

Ex. iso- No. W X Y Z A B M R² m.p. ° C. mer I-c-2 CH₃ CH₃ CH₃ H CH₃ H OC₂H₅ 201 α I-c-3 H CH₃ CH₃ H CH₃ H O C₂H₅ 122 α I-c-4 H CH₃ CH₃ H CH₃ HO C₂H₅ 197 β I-c-5 CH₃ CH₃ CH₃ CH₃ CH₃ H O C₂H₅ 211 β I-c-6 CH₃ CH₃ CN HCH₃ H O C₂H₅ 229 β I-c-7 H CH₃ CH₃ CH₃ CH₃ H O C₂H₅ 171 β I-c-8 H Cl BrH CH₃ H O C₂H₅ 201 β I-c-9 H CH₃ Cl H CH₃ H O C₂H₅ 198 β I-c-10 CH₃ CNCH₃ H CH₃ H O C₂H₅ 197 β I-c-11 CH₃ CH₃ Br H CH₃ H O C₂H₅ >220  β I-c-12H Cl Cl H CH₃ H O C₂H₅ 171 β I-c-13 H Cl C₂H₅ H CH₃ H O C₂H₅ 196 βI-c-14 CH₃ CH₃ Cl H CH₃ H O C₂H₅ 205 β I-c-15 H CH₃ H CH₃ CH₃ H O C₂H₅185 β I-c-16 CH₃ CH₃ CH₃ H CH₃ CH₃ O C₂H₅ 218 α I-c-17 H Cl CH₃ Cl CH₃ HO C₂H₅ 222 β I-c-18 H CH₃ Cl CH₃ CH₃ H O C₂H₅ 206 β I-c-19 H Br CH₃ CH₃CH₃ H O C₂H₅ 159–160 β I-c-20 Br C₂H₅ Br H CH₃ H O C₂H₅ β

EXAMPLE (II-1)

At 30 to 40° C., 27.8 g of the compound of Example (XXIII-1) in 180 mlof methylene chloride are added dropwise to 45.4 g of concentratedsulphuric acid, and the mixture is stirred for another 2 hours at 30 to40° C. 64 ml of anhydrous methanol are then added dropwise, and themixture is stirred for another 6 hours at 40 to 70° C. The mixture isthen poured onto 0.46 kg of ice and extracted with methylene chloride,and the organic phase is washed with aqueous NaHCO₃ solution, dried andconcentrated. The residue is recrystallized from MTB ether/n-hexane.

Yield 19.80 g (64% of theory), m.p.: 101° C.

EXAMPLE (II-2)

At 0 to 10° C., 19.6 g of mesityleneacetyl chloride in 20 ml ofanhydrous THF are added dropwise to 20.98 g of the compound of Example(XIII-1) and 30.8 ml (0.22 mol) of triethylamine in 200 ml of anhydrousTHF, and the mixture is stirred at room temperature until the reactionhas ended. The mixture is filtered off with suction, the filter cake isrinsed and the filtrate is concentrated. The residue is taken up inmethylene chloride, washed with 200 ml 1 N HCl, dried and concentrated.Silica gel column chromatography using cyclohexane/ethyl acetate 2/1gives 24.0 g (72% of theory). ¹H NMR (200 MHz, CDCl₃): δ=1.12 (d, 3H,CH—CH ₃), 3.51 (α), 3.6 (β) (2s, 2H, CH ₂, CONH, β/α approximately 3:1),3.71, 3.75 (α/β) (2s, 3H, CO₂CH₃, (β/α 3:1), 6.90 (α), 6.92 (β) (2s, 2H,ArH).

Similar to this method, and/or according to the general preparationprocedures, the following compounds of the formula (II) are obtained:

TABLE 5 (II)

Ex. iso- No. W X Y Z A B R⁸ m.p. ° C. mer II-3 H CH₃ CH₃ H CH₃ H CH₃  71α II-4 H CH₃ CH₃ H CH₃ H CH₃ β⁽¹⁾ II-5 CH₃ CH₃ CH₃ H CH₃ CH₃ CH₃ 106 αII-6 H CH₃ CH₃ H CH₃ CH₃ CH₃  96 α II-7 C₂H₅ C₂H₅ CN H CH₃ H CH₃ β⁽²⁾II-8 H Cl Cl H CH₃ H CH₃ β⁽³⁾ II-9 H Cl CH₃ H CH₃ H CH₃ β⁽⁴⁾ II-10 CH₃Cl Cl H CH₃ H CH₃  125– β 127 II-11 Cl Cl CH₃ H CH₃ H CH₃ 171 β II-12 HCl C₂H₅ H CH₃ H CH₃ β⁽⁵⁾ II-13 CH₃ CH₃ CN H CH₃ H CH₃ 111 β II-14 CH₃CH₃ CH₃ CH₃ CH₃ H CH₃ 150 β II-15 H CH₃ CH₃ CH₃ CH₃ H CH₃ 122 β II-16CH₃ CH₃ H Cl CH₃ H CH₃ 159 β II-17 H CH₃ Cl H CH₃ H CH₃ 160 β II-18 HCH₃ CH₃ CH₃ CH₃ H CH₃ 141 β II-19 H Cl Br H CH₃ H CH₃ 134 β II-20 CH₃ ClBr H CH₃ H CH₃ 164 β II-21 CH₃ CH₃ Cl H CH₃ H CH₃ 118 β II-22 CH₃ CN CH₃H CH₃ H CH₃ 135 β II-23 CH₃ CH₃ Br H CH₃ H CH₃ 156 β II-24 CH₃ Br Cl HCH₃ H CH₃ 150 β II-25 H CH₃ H CH₃ CH₃ H CH₃ 117 β II-26 Br Br C₂H₅ H CH₃H CH₃ 141 β II-27 Cl Cl Cl H CH₃ H CH₃ 156 β II-28 Br Br i-C₃H₇ H CH₃ HCH₃ 126 β II-29 H Cl Cl CH₃ CH₃ H CH₃  150– β 152 II-30 H Cl CH₃ Cl CH₃H CH₃  118– β 120 II-31 H CH₃ Cl CH₃ CH₃ H CH₃  144– β 146 II-32 H BrCH₃ Br CH₃ H CH₃  138– β 140 II-33 H CH₃ Cl Cl CH₃ H CH₃ 146 β ⁽¹⁾¹H NMR(200 MHz, CDCl₃): 1.12 (d, 3H, CHCH ³ ), 2.24 (α), 2.28 (β), (2s, 3H,Ar-2-CH ³ ), 2.37 (s, 3H, Ar-4-CH₃), 3.49 (α), 3.55 (β), (2s, 2H,CH₂CONH), 3.62 (β), 3.65 (α), (2s, 3H, CO₂CH₃, α/β approximately 1:3)⁽²⁾¹H MNR (400 MHz, CDCl₃): δ = 1.13 (α), 1.14 (β), (2d, 3H, CHCH ³ );α/β approximately 1:3), 1.36 (t, 6H, (CH₂ CH ³ )₂), 2.70 (q, 4H, (CH ²—CH₃)₂), 7.40 (α), 7.42 (β), (2s, 2H, Ar—H, α/β approximately 1:3 ⁽³⁾¹HNMR (400 MHz, CDCl₃): δ = 1.15, 1.16(2d, 3H, CHCH ³ ), 3.67–3.71 (3s,5H, CH₂CONH, CO₂ CH ³ ), 7.21–7.32 (m, 2H, ArH), 7.4–7.45 (m, 1H, ArH)⁽⁴⁾¹H NMR (400 MHz, CDCl₃): δ = 1.14 (d, 3H, CHCH ³ ), 2.34 (s, 3H, ArCH³ ), 7.03–7.09 (m, 1H, Ar—H), 7.17–7.27 (m, 2H, Ar—H). ⁽⁵⁾¹H NMR (400MHz, CDCl₃): δ = 1.14 (2d, 3H, CHCH ³ ), 1.23 (t, 3H, CH₂ CH ³ ), 2.53(q, 2H, CH₂CH₃), 7.08–7.12 (m, 1H, ArH), 7.25–7.29 (m, 2H, Ar—H).

EXAMPLE (XIII-1)

At 0 to 5° C., 73.2 ml (0.87 mol) of thionyl chloride are added dropwiseto 92.3 g of the compound of Example (XVI-1) in 870 ml of anhydrousmethanol, and the mixture is stirred at approximately 0° C. for 30minutes and then at approximately 40° C. overnight. The mixture isfiltered, the filtrate is concentrated and the residue is stirred with alittle MTB ether, the mixture is filtered off with suction and thefilter cake is rinsed and dried.

Yield 87.0 g (86% of theory), m.p.: >220° C.

EXAMPLE (XVI-1)

122.8 g of the compound of the example below and 130 g of NaOH in 2.5 lof water are heated in an autoclave at 195° C. for 2 hours, the pressureincreasing to approximately 20 bar. The mixture is then concentrated toapproximately ⅓ of its volume, concentrated HCl is added at 0 to 10° C.until the pH is 5 to 6, the mixture is concentrated, the residue isboiled with methanol, the mixture is filtered off with suction and thefiltrate is concentrated.

Yield 92.3 g (86% of theory), m.p.: >220° C.

EXAMPLE Compound of the Formula

In an autoclave, a mixture comprising 76 g of3-methyl-tetrahydropyran-4-one, 71.9 g (1.468 mol) of sodium cyanide, 96g (1 mol) of ammonium carbonate, 1.32 l of concentrated ammonia solutionand 1.32 l of ethanol is stirred at 120° C. for 3 hours, the internalpressure increasing to approximately 60 bar (prior to heating, ⅔ of thedesired reaction pressure is applied). The mixture is concentrated,dried with toluene, boiled with methanol and filtered off with suction.The mother liquor is concentrated to 400 ml, and further solidcomponents are precipitated by addition of MTB ether and are filteredoff with suction. The mother liquor is concentrated. The combinedresidues are boiled in ethanol, the mixture is filtered off with suction(A) and the filtrate is concentrated (B). (A) and (B) are combined.

Yield 126.0 g (100% of theory).

EXAMPLE (XXIII-1)

At 0 to 10° C., 21.6 g of mesitylene acetyl chloride in 20 ml ofanhydrous THF are added dropwise to 15.6 g of the compound of Example(XXII-1) and 15.4 ml of triethylamine in 220 ml of anhydrous THF, andthe mixture is stirred at room temperature until the reaction has ended.The mixture is stirred into 0.6 l of ice-water and 0.2 l of 1 N HCl andfiltered off with suction, and the residue is taken up in methylenechloride. The solution is dried and concentrated and the residue isre-crystallized from MTB ether/n-hexane.

Yield 27.8 g (84% of theory), m.p.: 121° C.

Similar to this method, and/or according to the general preparationprocedures, the following compounds of the formula (XXIII) are obtained:

TABLE 6 (XXIII)

Ex. No. W X Y Z A B m.p. ° C. XXIII-2 H CH₃ CH₃ H CH₃ H 112 XXIII-3 CH₃CH₃ CH₃ H CH₃ CH₃ 127 XXIII-4 H CH₃ CH₃ H CH₃ CH₃ 118

EXAMPLE (XIV-1)

At 70° C., 99.3 g of 2-chloro-4-ethylphenylacetic acid and 109 ml (1.5mol) of thionyl chloride are stirred until the evolution of gas hasended. Excess thionyl chloride is removed at 50° C. under reducedpressure. The residue is distilled.

Yield 99.10 g (91% of theory), b.p. 121° C./0–35 mbar.

EXAMPLE (XVII-1)

102.5 g (16.9% strength, 0.05 mol) of the compound of Example (XVIII-1),14.1 g of KOH, 17.8 ml of water and 35.5 ml of methanol are heatedtogether under reflux for 5 hours. The mixture is then concentrated andthe residue is taken up in water. The solution is washed with ethylacetate and the aqueous phase is acidified using conc. HCl (pH 1). Theprecipitate is filtered off with suction and dried.

Yield 14.4 g (80.6% of theory), m.p.: 140–142° C.

Similar to this method, and/or according to the general preparationprocedures, the following compounds of the formula (XVII) are obtained:

TABLE 7 (XVII)

Ex. No. W X Y Z m.p. ° C. XVII-2 Br Cl C₂H₅ H 147 XVII-3 Cl Cl C₂H₅ H146 XVII-4 H Cl C₂H₅ H 89–91 XVII-5 H Br C₂H₅ H 109 XVII-6 Br Br i-C₃H₇H 154–155 XVII-7 H CH₃ Cl Cl 103

EXAMPLE (XVIII-1)

With cooling, 9.1 ml of 30% strength sodium methoxide are added dropwiseto 5 g (94.4% strength, 0.0119 mol) of the compound of Example (XIX-1)in 5 ml of methanol, and the mixture is stirred under reflux for 5hours. After cooling, 0.01 ml of concentrated sulphuric acid are addeddropwise, and the mixture is stirred under reflux for 1 hour. Themixture is then concentrated and the residue is taken up in water. Thesolution is extracted with methylene chloride, dried and concentrated.

Yield 1.80 g (43% of theory), oil.

Similar to this method, and/or according to the general preparationprocedures, the following compounds of the formula (XVIII) are obtained:

TABLE 8 (XVIII)

Ex. No. W X Y Z R⁸ b.p. ° C. (mbar) XVIII-2 Br Cl C₂H₅ H CH₃ 105 0.06XVIII-3 Cl Cl C₂H₅ H CH₃ 92–94 0.05 XVIII-4 H Cl C₂H₅ H CH₃  82 0.03XVIII-5 H Br C₂H₅ H CH₃ 135 0.15 XVIII-6 Br Br i-C₃H₇ H CH₃ oil* XVIII-7H CH₃ Cl Cl CH₃ oil* *After chromatographic purification, thesecompounds were directly reacted to give the corresponding acids of theformulae (XVII-6) and (XVII-7).

EXAMPLE (XIX-1)

1400 ml (17.4 mol) of 1,1-dichloroethane and then 320 g (1.147 mol) ofthe compound of Example (XX-1) in 342 ml of anhydrous acetonitrile areadded dropwise to 208 ml (1.746 mol) of butyl nitrite in 684 ml ofanhydrous acetonitrile. The mixture is stirred at room temperatureovernight and then poured into 4.6 l of 20% strength HCl. The mixture isextracted with MTB ether and the organic phase is washed with 2 l ofwater, dried and concentrated.

Yield 434 g. The crude product reacted further without any furtherpurification.

Similar to this method, and/or according to the general preparationprocedures, the following compounds of the formula (XIX) are obtained:

TABLE 9 (XIX)

Ex. No. W X Y Z XIX-2 Br Cl C₂H₅ H oil* XIX-3 Cl Cl C₂H₅ H oil* XIX-4 HCl C₂H₅ H 011* XIX-5 H Br C₂H₅ H GC/MS: 314, 316, 318 12%, 14%, 12% 199(100%) 197(98%) XIX-6 Br Br i-C₃H₇ H oil* XTX-7 H CH₃ Cl Cl oil* *Thecrude mixtures were directly employed for the alcoholysis for preparingthe compounds of the formula (XVIII).

EXAMPLE (XX-1)

At 10–30° C., 397 g (2.48 mol) of bromine in 744 ml of glacial aceticacid are added dropwise to 150 g (1.24 mol) of 4-ethylaniline in 1990 mlof glacial acetic acid, and the mixture is stirred at 30° C. for another3 hours. The mixture is then diluted with water and made alkaline using25% strength ammonia solution. The precipitate is filtered off withsuction, taken up in methylene chloride, dried and concentrated.

Yield 320.0 g (93% of theory), m.p.: 74° C.

EXAMPLE (XX-2)

Using the method of Example (XX-1) the compound of the formula

is obtained

M.p.: 48° C.

EXAMPLE (XXII-1)

At room temperature, 30.5 g (0.27 mol) of 2-methyl-tetrahydropyran-4-one(preparation see further below) are added dropwise to a mixturecomprising 50.9 g (0.75 mol) of 25% strength ammonia solution, 17.2 g(0.32 mol) of ammonium chloride and 15.7 g (0.32 mol) of sodium cyanidein 48 ml of water and the mixture is stirred at 45° C. overnight.Customary work-up gives 29.1 g (77% of theory) of the end product as anoil.

EXAMPLE (XXII-2)

This compound is obtained in a similar manner as a brown oil.

EXAMPLE Compound of the Formula

At a temperature of approximately 100° C., 364.37 g of the compound ofthe formula ClCH₂CH₂COCH₂CHClCH₃ (preparation see the next example) areadded dropwise over a period of approximately 75 minutes to 552.72 g(3.54 mol) of NaH₂PO₄×2H₂O and 179.7 g (1.55 mol) of 85% strengtho-phosphoric acid in 5500 ml of water, and the mixture is stirred at100° C. for a further 8 hours.

The mixture is cooled to approximately 0° C. and 10 molar NaOH is addeddropwise until a pH of 5 to 6 is reached. 1500 ml of methylene chlorideare added and the resulting salt is filtered off with suction and theaqueous phase is extracted 3× with 1000 ml of methylene chloride eachtime. The organic phase is dried, concentrated and distilled.

Yield: 119.6 g (55% of theory), b.p.: 62° C./15 mbar.

EXAMPLE Compound of the Formula ClCH₂CH₂COCH₂CHClCH₃

At room temperature, 507.88 g of 3-chloropropionyl chloride are addeddropwise over a period of 15 minutes to 758.08 g (5.6 mol) of AlCl₃ in560 ml of methylene chloride, and 189 g (4.5 mol) of propylene areintroduced into this mixture at approximately 28 to 30° C. over a periodof approximately 3 hours.

The reaction mixture is decanted off from excess AlCl₃ and, at 0 to 10°C., slowly added dropwise to a mixture of 508 ml of methylene chlorideand 2032 ml of 1N HCl.

The organic phase is separated off, washed 3 times with 500 ml of watereach time, dried and concentrated.

Yield: 470 g (70% of theory).

USE EXAMPLES Example A

Myzus Test

Solvent: 7 parts by weight of dimethylformamide Emulsifier: 1 part byweight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amount of solvent and thestated amount of emulsifier, and the concentrate is diluted with waterto the desired concentration.

Cabbage leaves (Brassica oleracea) which are heavily infested by peachaphids (Myzus persicae) are treated by being dipped into the preparationof active compound of the desired concentration.

After the desired period of time, the kill in % is determined. 100%means that all aphids have been killed; 0% means that none of the aphidshave been killed.

In this test, at an exemplary active compound concentration of 0.1%, forexample the compounds of Examples I-a-9, I-a-10, I-a-12, I-a-14, I-a-15,I-a-16, I-c-8, I-b-17, I-a-18, I-a-19, I-a-20, I-a-21, I-c-11 and I-c-12effected a kill of in each case 100% after 6 days.

Example B

Nephotettix Test

Solvent: 20 parts by weight of dimethylformamide Emulsifier:  1 part byweight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amount of solvent and thestated amount of emulsifier, and the concentrate is diluted with waterto the desired concentration.

Rice seedlings (Oryzae sativa) are treated by being dipped into thepreparation of active compound of the desired concentration and arepopulated with green rice leaf hoppers (Nephotettix cincticeps) whilethe seedlings are still moist.

After the desired period of time, the kill in % is determined. 100%means that all leaf hoppers have been killed; 0.1% means that none ofthe leaf hoppers have been killed.

In this test, at an exemplary active compound concentration of 0.1%, forexample the compounds of Examples I-b-2, I-b-4, I-c-3, I-b-5, I-b-1,I-c-1, I-b-6, I-b-7, I-c-4, I-a-7, I-b-8, I-b-11, I-c-5, I-c-7, I-b-17,I-c-11, I-a-22, I-b-22, I-b-23 and I-b-24 effected in each case a killof 100% after 6 days.

Example C

Phaedon Larvae Test

Solvent: 7 parts by weight of dimethylformamide Emulsifier: 1 part byweight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amount of solvent and thestated amount of emulsifier, and the concentrate is diluted with waterto the desired concentration.

Cabbage leaves (Brassica oleracea) are treated by being dipped into thepreparation of active compound of the desired concentration and arepopulated with larvae of the mustard beetle (Phaedon cochleariae) whilethe leaves are still moist.

After the desired period of time, the kill in % is determined. 100%means that all beetle larvae have been killed; 0% means that none of thebeetle larvae have been killed.

In this test, at an exemplary active compound concentration of 0.1%, forexample the compounds of Examples I-b-8, I-b-22, I-b-23, I-c-13, I-b-4,I-c-3, I-a-7 and I-a-8 effected a kill of in each case 100% after 7days.

Example D

Spodoptera frugiperda Test

Solvent: 7 parts by weight of dimethylformamide Emulsifier: 1 part byweight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amount of solvent and thestated amount of emulsifier, and the concentrate is diluted with waterto the desired concentration.

Cabbage leaves (Brassica oleracea) are treated by being dipped into thepreparation of active compound of the desired concentration and arepopulated with caterpillars of the owlet moth (Spodoptera frugiperda)while the leaves are still moist.

After the desired period of time, the kill in % is determined. 100%means that all caterpillars have been killed; 0% means that none of thecaterpillars have been killed.

In this test, at an exemplary active compound concentration of 0.1%, forexample the compounds of Examples I-c-3, I-a-14, I-c-15, I-a-20, I-c-13and I-b-24 effected a kill of in each case 100% after 7 days.

Example E

Tetranychus Test (OP-Resistant/Dip Treatment)

Solvent: 3 parts by weight of dimethylformamide Emulsifier: 1 part byweight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amount of solvent and thestated amount of emulsifier, and the concentrate is diluted with waterto the desired concentration.

Bean plants (Phaseolus vulgaris) which are heavily infested by allstages of the greenhouse red spider mite Tetranychus urticae are dippedinto a preparation of active compound of the desired concentration.

After the desired period of time, the kill in % is determined. 100%means that all spider mites have been killed; 0% means that none of thespider mites have been killed.

In this test, at an exemplary active compound concentration of 0.1%, forexample the compounds of Examples I-b-2, I-b-3, I-b-4, I-c-3, I-a-4,I-c-1, I-b-7, I-c-4, I-a-7, I-a-9 and I-b-8 had an effect of in eachcase 100% after 14 days, and the compounds of Examples I-b-15, I-b-16,I-b-17, I-b-22 and I-c-13 had this effect at an exemplary activecompound concentration of 0.02%.

Example F

Critical Concentration Test/Root-Systemic Action

Test insect: Aphis fabae Solvent: 4 parts by weight of acetoneEmulsifier: 1 part by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amount of solvent and thestated amount of emulsifier, and the concentrate is diluted with waterto the desired concentration.

The preparation of active compound is intimately mixed with soil. Theconcentration of the active compound in the preparation is ofpractically no importance here, only the amount by weight of activecompound per unit volume of soil, which is given in ppm (=mg/l), beingdecisive. The treated soil is transferred into pots and these areplanted with pregerminated broad beans. The active compound can in thisway be taken up from the soil by the roots of the plants and betransported into the leaves.

To demonstrate the root-systemic effect, the leaves are populated withthe above-mentioned test animals after 7 days. After a further 6 days,evaluation is carried out by counting or estimating the dead animals.The root-systemic action of the active compound is deduced from themortality figures. It is 100% if all the test animals have been killedand 0% if just as many test insects are still alive as in the case ofthe untreated control.

In this test, at an exemplary active compound concentration of 20 ppm,for example the compounds of Examples I-a-1, I-b-4, I-a-4, I-b-5,I-a-16, I-b-1, I-b-3, I-c-1, I-c-2, I-b-17, I-b-10, I-a-16 and I-b-25had an effect of in each case 100%.

Example G

Critical Concentration Test/Root-systemic Action

Test insect: Myzus persicae Solvent: 4 parts by weight of acetoneEmulsifier: 1 part by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amount of solvent and thestated amount of emulsifier, and the concentrate is diluted with waterto the desired concentration.

The preparation of active compound is intimately mixed with soil. Theconcentration of the active compound in the preparation is ofpractically no importance here, only the amount by weight of activecompound per unit volume of soil, which is given in ppm (=mg/l), beingdecisive. The treated soil is transferred into pots and these areplanted with peppers at the cotyledon stage. The active compound can inthis way be taken up from the soil by the roots of the plants and betransported into the leaves.

To demonstrate the root-systemic effect, the leaves are populated withthe above-mentioned test animals after 7 days. After a further 6 days,evaluation is carried out by counting or estimating the dead animals.The root-systemic action of the active compound is deduced from themortality figures. It is 100% if all the test animals have been killedand 0% if just as many test insects are still alive as in the case ofthe untreated control.

In this test, at an exemplary active compound concentration of 20 ppm,for example the compounds of Examples I-b-10, I-a-16 and I-b-25 had aneffect of in each case 100%.

1. A compound of the formula (XVII)

in which X¹ represents fluorine, chlorine or bromine, Y¹ representsethyl and W¹ represents hydrogen, fluorine, chlorine or bromine.
 2. Acompound of the formula (XVIII)

in which X¹ represents fluorine, chlorine or bromine, Y¹ representsethyl W¹ represents hydrogen, fluorine, chlorine or bromine, and R⁸represents alkyl.
 3. The compound of claim 2 wherein R⁸ is C₁–C₆-alkyl.4. The compound of claim 3 wherein R⁸ is methyl or ethyl.
 5. A compoundof the formula (XIX)

in which X represents fluorine, chlorine or bromine, Y represents ethyl,W represents hydrogen, fluorine, chlorine or bromine, and Z representsrepresents hydrogen, halogen, alkyl, alkoxy, halogenoalkyl,halogenoalkoxy, hydroxyl, cyano, nitro or represents phenoxy,phenylthio, 5- or 6-membered hetaryloxy, 5- or 6-membered hetarylthio,phenylalkyloxy or phenylalkylthio, each of which is optionallysubstituted.
 6. The compound of claim 5 wherein Z represents hydrogen,halogen, C₁–C₆-alkyl, C₁–C₆-alkoxy, C₁–C₄-halogenoalkyl,C₁–C₄-halogenoalkoxy, hydroxyl, cyano, nitro or represents phenoxy,phenylthio, thiazolyloxy, pyridinyloxy, pyrimidyloxy, pyrazolyloxy,phenyl-C₁–C₄-alkyloxy or phenyl-C₁–C₄-alkylthio, each of which isoptionally substituted by halogen, C₁–C₄-alkyl, C₁–C₄-alkoxy,C₁–C₄-halogenoalkyl, C₁–C₄-halogenalkoxy, nitro or cyano.